Thermoplastic elastomeric copolymers and hair and skin care compositions containing the same

ABSTRACT

The present invention relates to water or alcohol soluble or dispersible thermoplastic elastomeric copolymers and to cosmetic and pharmaceutical compositions containing these copolymers. This invention especially relates to copolymers useful for hair styling purposes, and to hair styling compositions containing these copolymers. This invention further relates to copolymers useful for providing cosmetic and pharmaceutical compositions for topical application to the skin. These topical skin care compositions are useful for delivereing and/or transdermally transporting active ingredients to or thorugh the skin.

This is a file-wrapper continuation of application Ser. No. 08/440,852,filed on May 15, 1995, abandoned which is a file-wrapper continuation ofapplication Ser. No. 08/259,070, filed on Jun. 20, 1994 (abandoned),which is a continuation-in-part of application Ser. No. 08/257,962,filed on Jun. 16, 1994, abandoned which is a contuation-in-part ofapplication Ser. No. 08/231,955, filed on Apr. 21, 1994 (abandoned),which is a continuation of application Ser. No. 08/086,605, filed onJul. 1, 1993 (abandoned).

TECHNICAL FIELD

The present invention relates to water or alcohol soluble or dispersiblethermoplastic elastomeric copolymers and to cosmetic and pharmaceuticalcompositions containing these copolymers. These copolymers are usefulfor hair setting and styling purposes. A particularly useful applicationfor these copolymers is in hair spray and mousse compositions. Thisinvention further relates to copolymers useful for incorporating intocosmetic and pharmaceutical compositions for topical application to theskin. Skin care compositions containing these copolymers are useful fordelivering and/or transdermally transporting a wide variety of activeingredients to and/or through the skin.

BACKGROUND OF THE INVENTION

In the hair care area, the desire to have hair retain a particular styleor shape is widely held. Such style retention is generally accomplishedby either of two routes: permanent chemical alteration of the hair fiberor temporary alteration of hair style or shape. A temporary alterationis one which can be removed by water or by shampooing. Temporary stylealteration has generally been accomplished by application of acomposition to dampened hair after shampooing and/or conditioning andprior to drying and/or styling. Products in the form of mousses, gels,lotions, or sprays are most commonly used for this purpose. Once thedesired style is achieved, spray products are commonly used to helpretain the style. These various hair care products utilize a variety ofgums and resins for providing styling and retention. However, the gumsand resins currently used tend to feel either too sticky or too stiffupon the hair. Also, these gums and resins do not wash out as easily asdesired. Therefore, the need exists for improved styling and styleretention materials which provide a strong, lasting, hold without beingeither too stiff or too sticky, and yet which are easily removed byshampooing. Furthermore, because most hair care styling compositions arewater and/or alcohol based, it is necessary that these materials havegood solubility or dispersibility in these bases.

Thermoplastic elastomeric copolymers are well known. These copolymerscombine thermoplastic properties, which give them solubility andstrength, with rubber-like elastic properties, which give themflexibility and shape retention. However, despite these highly desirableproperties, most thermoplastic elastomeric copolymers are generallyinsoluble or poorly soluble in water and/or alcohol systems and wouldnot be suitable in hair care compositions. Therefore, thermoplasticelastomeric copolymers having good water and/or alcohol solubility wouldbe useful for developing improved hair care compositions.

In the present invention new classes of thermoplastic elastomericcopolymers have been developed which have the desired flexibility,strength, and elastic properties and yet are readily soluble and/ordispersible in water and/or alcohol systems. Furthermore, thesematerials provide hair care compositions which leave the hair feelingnatural, i.e. not stiff.

In addition to the hair care benefits provided by these copolymers, ithas been found that these materials are also useful for incorporationinto a wide variety of cosmetic and pharmaceutical compositions fortopical application to the skin. These copolymers provide topicalcompositions which are more easily and uniformly spread upon the skin,which feel good upon the skin, and yet which are highly substantive.Furthermore, these copolymers are useful for enhancing the penetrationof a wide variety of cosmetic and pharmaceutical actives into the skin,or alternatively, through the skin for systemic delivery.

It is an object of the present invention to provide novel, water and/oralcohol soluble and/or dispersible thermoplastic elastomeric copolymers.

It is another object of the present invention to provide novelthermoplastic elastomeric copolymers useful in hair care compositions.

It is another object of the present invention to provide novel hair carecompositions having improved styling and/or hold properties and havingimproved aesthetics.

It is another object of the present invention to provide novelthermoplastic elastomeric copolymers useful in topical skin carecosmetic and pharmaceutical compositions.

It is another object of the present invention to provide novel topicalcosmetic and pharmaceutical compositions useful for delivering a widevariety of cosmetic materials and pharmaceutical actives to and/orthrough the skin.

These and other objects will become readily apparent from the detaileddescription which follows.

SUMMARY OF THE INVENTION

The present invention relates to a water or alcohol soluble ordispersible thermoplastic elastomeric copolymer having a backbone andtwo or more polymeric pendant side chains, said copolymer formed fromthe copolymerization of randomly repeating A and B units wherein saidcopolymer comprises:

(i) from about 40% to about 90% by weight of said A units, wherein saidA units are polymerizable monomer units; and

(ii) from about 10% to about 60% by weight of said B units, wherein saidB units are hydrophilic macromonomer units copolymerizable with A,whereby said macromonomer units form said pendant polymeric side chains;

wherein said copolymer has a weight average molecular weight greaterthan about 10,000, and wherein said copolymer exhibits two distinctT_(g) values, said first T_(g) corresponding to said backbone and havinga value less than about 0° C., and said second T_(g) corresponding tosaid side chains and having a value greater than about 25° C.

The present invention also relates to a water or alcohol soluble ordispersible thermoplastic elastomeric copolymer having a backbone andtwo or more polymeric side chains, said copolymer formed from thecopolymerization of randomly repeating A and B units and correspondingto the formula

    [A].sub.a [B].sub.b

wherein A is at least one polymerizable monomer unit corresponding tothe formula ##STR1## wherein X is selected from the group consisting of--OH, --OM, --OR⁴, --NH₂, --NHR⁴, and --N(R⁴)₂ ; M is a cation selectedfrom the group consisting of Na+, K+, Mg++, Ca++, Zn++, NH₄ +,alkylammonium, dialkylammonium, trialkylammonium, and tetralkylammonium;each R⁴ is independently selected from the group consisting of H, C₁ -C₈straight or branched chain alkyl, N,N,-dimethylaminoetpyl,2-hydroxyethyl, 2-methoxyethyl, and 2-ethoxyethyl; and R⁵ and R⁶ areindependently selected from the group consisting of H, C₁ -C₈ straightor branched chain alkyl, methoxy, ethoxy, 2-hydroxyethoxy,2-methoxyethyl, and 2-ethoxyethyl.

B is at least one hydrophilic macromonmer unit copolymerizable with Acorresponding to the formula ##STR2## wherein E is an ethylenicallyunsaturated moiety, copolymerizable with A, selected from the groupconsisting of vinyl, allyl, acryloyl, methacryloyl, ethacryloyl,3-vinylbenzoyl, and 4-vinylbenzoyl; R and R' are independently selectedfrom the group consisting of H and C₁ -C₈ straight or branched chainalkyl; m is an integer from about 10 to about 2000; a is an integer ofabout 100 or greater; and b is an integer of about 2 or greater.

In further embodiments, B is at least one hydrophilic macromonomer unitcopolymerizable with A corresponding to the formula ##STR3## wherein Rand R' are independently selected from the group consisting of H and C₁-C₈ straight or branched chain alkyl; m is an integer from about 10 toabout 2000; a is an integer of about 100 or greater; and b is an integerof about 2 or greater.

In further embodiments, B is at least one hydrophilic macromonmer unitcopolymerizable with A corresponding to the formula ##STR4## wherein Eis an ethylenically unsaturated moiety, copolymerizable with A, selectedfrom the group consisting of vinyl, allyl, acryloyl, methacryloyl,ethacryloyl, 3-vinylbenzoyl, and 4-vinylbenzoyl, and mixtures thereof;R" is selected from the group consisting of C₁ -C₄₀ straight or branchedchain alkyl; R₃ is selected from the group consisting of H, and C₁ -C₈straight or branched chain alkyl; m is an integer from about 20 to about2000; a is an integer of about 100 or greater; and b is an integer ofabout 2 or greater.

In further embodiments, B is at least one hydrophilic macromonomer unitcopolymerizable with A corresponding to the formula ##STR5## wherein Eis an ethylenically unsaturated moiety, copolymerizable with A, selectedfrom the group consisting of vinyl, allyl, acryloyl, methacryloyl,ethacryloyl, 2-vinyl benzyl, 3-vinyl benzyl, 4-vinyl benzyl, andmixtures thereof; R¹² is selected from the group consisting of hydrogen,C1-6 straight or branched chain alkyl, benzyl, 1-phenyl substituted C2-6straight or branched chain alkyl, 1,1 -diphenyl substituted C2-6straight or branched chain alkyl, and mixtures thereof; P is a polarmoiety selected from the group consisting of 2-pyridyl, 3-pyridyl,4-pyridyl, halogen substituted 2-, 3-, or 4-pyridyl, C1-4 alkylsubstituted 2-, 3-, or 4-pyridyl, 2-aminophenyl, 3-aminophenyl,4-aminophenyl, 2-aminomethylphenyl, 3-aminomethylphenyl,4-aminomethylphenyl, 2-aminoethylphenyl, 3-aminoethylphenyl, and4-aminoethylphenyl, and pharaceutically acceptagle salts and quaternizedderivatives thereof, and mixtures thereof; and m is an integer fromabout 20 to about 2000.

Infurther embodiments, B is at least one hydrophilic macromonomer unitcopolymerizable with A and C corresponding to the formula ##STR6##wherein E is an ethylenically unsaturated moiety, copolymerizable withA, selected form the group consisting of vinyl, allyl, acryloyl,methacryloyl, ethacryloyl, 2-vinyl benzyl, 3-vinyl benzyl, 4-vinylbenzyl, and mixtures thereof; R¹² is selected from the group consistingof hydrogen, C1-C6 straight or branched chain alkyl, benzyl, 1-phenylsubstituted C2-6 straight or branched chain alkyl, 1,1-diphenylsubstituted C2-6 straight or branched chain alkyl, and mixtures thereof;and R¹³ is selected from the group consisting of H and C1-6 straight orbranched chain alkyl, and R¹⁴, and R¹⁵ are independently selected formthe group consisting of C1-8 straight or branched chain alkyl; and m isis an integer from about 20 to about 2000.

In further embodiments, the present invention relates to hair carecompositions, especially hair setting and styling compositions,containing these copolymers.

In further embodiments, the present invention relates to cosmetic andpharmaceutical compositions containing these copolymers for topicalapplication to the skin for the delivery of cosmetic materials andpharmaceutical actives onto, into and/or through the skin.

All percentages and ratios used herein are by weight of the totalcomposition and all measurements made are at 25° C., unless otherwisedesignated. The invention hereof can comprise, consist of, or consistessentially of, the essential as well as optional ingredients andcomponents described herein.

DETAILED DESCRIPTION OF THE INVENTION

The term "thermoplastic elastomeric copolymer" as used herein means thatthe copolymer has both thermoplastic and elastomeric properties. Theterm "thermoplastic elastomeric copolymer" is one familiar to those ofordinary skill in polymer science. By "thermoplastic" is meant that uponheating, the copolymer softens and upon cooling it rehardens; upon beingsubject to stress it begins to flow and upon removal of stress it stopsflowing. By "elastomeric" is meant that the copolymer has an elasticmodulus such that the copolymer exhibits a resistance to deformation andhas limited extensibility and retraction. In other words, the copolymertends to recover its size and shape after deformation.

The term "macromonomer" is one familiar to those of ordinary skill inpolymer science, and is used to describe a polymeric material containinga polymerizable moiety. A macromonomer is a macromolecular monomer. Amacromonomer is essentially a very large type of monomer building blockunit which can be used in a polymerization reaction to form polymerswith itself, with other monomers, or with other macromonomers.

The term "water or alcohol soluble or dispersible" as used herein meansthat these copolymers are either freely soluble in or dispersible (as astable suspension) in at least one of the following solvents, oralternatively, in any combination of one of the following solvents:water, methanol, ethanol, and isopropanol. By "soluble" is meant thatthe copolymer is soluble in the solvent or solvents at 25° C. at aconcentration of at least about 20 mg/mL, more preferably about 50mg/mL, and most preferably about 100 mg/mL. By "dispersible" is meantthat the copolymer forms a stable, uniform suspension (without theaddition of further materials such as emulsifiers) when combined withthe solvent or solvents at 25° C. at a concentration of at least about20 mg/mL, more preferably about 50 mg/mL, and most preferably about 100mg/mL.

Thermoplastic Elastomeric Copolymers

The copolymers of the present invention are characterized in having anelastomeric or flexible backbone and rigid, thermoplastic, hydrophilicside chains. This combination of both elastomeric and thermoplasticmoieities in a single copolymer provides the unique and usefulproperties of these materials. The copolymers of the present invention,can also be referred to as "graft copolymers" because they can beprepared from the copolymerization of monomer units and macromonmerunits. In other words, the macromonomer is "grafted" or incorporatedinto the copolymer.

These copolymers exhibit two distinct immiscible phases. Without beinglimited by theory, it is believed that the hydrophilic side chains ofthese copolymers are closely associated with each other, therebyexisting in one phase, while the backbone of the copolymer remains in aseparate phase. A consequence of this phase immiscibility is that thesecopolymers exhibit two distinct glass transition temperatures or, "T_(g)'s", for the backbone and the side chains. T_(g) is a well known term ofart in polymer science used to describe the temperature at which apolymer or portion thereof undergoes a transition from a solid orbrittle material to a liquid or rubber-like material. Glass transitiontemperatures can be measured using standard techniques that are wellknown to the polymer scientist of ordinary skill in the art. Oneparticularly useful technique for determining glass transitions isdifferential scanning calorimetry (also known as DSC). The glasstransition phenomenon in polymers is described in Introduction toPolymer Science and Technology: An SPE Textbook, (eds. H. S. Kaufman andJ. J. Falcetta), (John wiley & Sons: 1977), which is incorporated byreference herein in its entirety.

The T_(g) of the backbone of the copolymers herein (i.e. that part ofthe copolymer not containing the side chains) should be less than about0° C. Preferably the T_(g) of the backbone should be from about -10° C.to about -130° C., more preferably from about -20° C. to about -125° C.,and most preferably from about -55° C. to about -120° C. The T_(g) ofthe side chain of the copolymers (i.e. that part of the copolymer notcontaining the backbone) is greater than about 20° C. Preferably theT_(g) of the sidechain should be from about 25° C. to about 200° C.,more preferably from about 30° C. to about 175° C., and most preferablyfrom about 35° C. to about 150° C.

Because these copolymers possess two distinct T_(g) 's, these copolymersare useful in hair styling and setting compositions. Without beinglimited by theory, it is believed that when these copolymers aresubjected to temperatures above both T_(g) 's, they are essentiallyliquid and can provide great flexibility during the styling process(e.g., when curling irons, blow driers, and other heat sources areapplied to the hair). Upon cooling of the copolymer to room temperature(e.g. when the heat source is removed from the hair) the copolymer isthen at a temperature that is typically between both T_(g) 's, and thecopolymer possesses structural rigidity from the macromonomer sidechains, and yet has flexibility from the backbones, and can provide astrong, yet flexible, hair hold or style retention.

Furthermore, at skin temperatures, these copolymers would be at atemperature which is essentially between both T_(g) 's. These copolymerscan enhance the film forming properties of skin care compositions, andprovide benefits shuch as better and more even distribution upon theskin.

The copolymers of the present invention are formed from thecopolymerization of randomly repeating A and B units, preferably whereinthe A units are selected from at least one polymerizable, ethylenicallyunsaturated monomer unit, and the B units are selected from at least onehydrophilic macromonomer unit which contains an ethylenicallyunsaturated moiety which is copolymerizable with A. In typicalembodiments of these copolymers, the backbone is primarily derived fromthe ethylenically unsaturated portion of the A monomer unit and theethylenically unsaturated portion of the B macromonomer unit. The sidechains are derived from the non-copolymerized portions of themacromonomer. The A and B units can be selected from a wide vairety ofstructures as long as the limitations of the copolymer are met (e.g.,solubility, T_(g) 's, and molecular weights).

The A monomer units of the copolymers of the present invention cancomprise from about 40% to about 90%, more preferably from about 50% toabout 85%, and most preferably from about 60% to about 80%, by weight,of the copolymers.

The hydrophilic B macromonomer units can comprise from about 10% toabout 60%, more preferably from about 15% to about 50%, and mostpreferably from about 20% to about 40%, by weight of the copolymers.

The copolymers of the present invention have a weight average molecularweight of at least about 10,000. There is no upper limit for molecularweight except that which limits applicability of the invention forpractical reasons, such as viscosity, processing, aestheticcharacteristics, formulation compatibility, etc. In general, the weightaverage molecular weight is less than about 5,000,000, more generallyless than about 2,500,000, and typically less than about 1,500,000.Preferably, the weight average molecular weight is from about 10,000 toabout 5,000,000, more preferably from about 75,000 to about 1,000,000,even more preferably from about 100,000 to about 850,000, and mostpreferably from about 125,000 to about 750,000.

Alternatively, the copolymers of the present invention can also berepresented by the formula

    [A].sub.a [B].sub.b

wherein A and B are as described herein, and where a is an integer ofabout 100 or greater, preferably a is an integer from about 100 to about3000, more preferably from about 250 to about 2000, and most preferablyfrom about 350 to about 1500, and b is an integer of about 2 or greater,preferably from about 2 to about 50, more preferably from about 2 toabout 20, and most preferably from about 2 to about 10. In this formula,it is expressly intended that even though ranges are provided for thesubscripts a and b, these subscripts are not intended to strictly limitthe polymers herein so long as the physical propoerties of the polymersare achieved. When the copolymers herein are described by the formuladisclosed in this paragraph it has been found useful to describe thecopolymers by their number average molecule weights. In general, thenumber average molecular weight is less than about 2,500,000, moregenerally less than about 1,500,000, and typically less than about1,000,000. Preferably, the number average molecular weight is from about15,000 to about 1,000,000, more preferably from about 20,000 to about500,000, and most preferably from about 25,000 to about 250,000.

By appropriate selection and combination of the particular A and B unitsand by the choice of specific relative ratios of the units well withinthe ability of one of ordinary skill in the art, the copolymers can beoptimized for various physical properties such as solubility, T_(g) 's,and the like, and for compatibility with other ingredients commonly usedin hair care and skin care applications.

When the copolymers of the present invention are incorporated into hairand/or skin care compositions, the copolymers typically comprise fromabout 0.1% to about 25%, preferably from about 0.5% to about 20%, morepreferably from about 1% to about 10%, and most preferably from about 2%to about 5% of the composition, although higher or lower amounts can beused depending upon the particular application.

Monomer "A" Units

The "A" monomer unit is selected from polymerizable monomers, preferablyethylenically unsaturated monomers. Either a single A monomer orcombinations of two or more A monomers can be utilized. For example, iftwo different A monomers are polymerized with a B macromonomer, theresulting copolymer could be described as a terpolymer. In either case,the monomers are selected to meet the requirements of the copolymer. By"polymerizable", as used herein, is meant monomers that can bepolymerized using any conventional synthetic techniques. Monomers thatare polymerizable using conventional free radical initiated techniquesare preferred. The term "ethylenically unsaturated" is used herein tomean monomers that contain at least one polymerizable carbon-carbondouble bond (which can be mono-, di-, tri-, or tetra-substituted).

The A monomer units of the copolymers of the present invention cancomprise from about 40% to about 90%, more preferably from about 50% toabout 85%, and most preferably from about 60% to about 80%, by weight,of the copolymers.

The ethylenically unsaturated A monomer units preferably can bedescribed by the following formula ##STR7## wherein X is selected fromthe group consisting of --OH, --OM, --OR⁴, --NH₂, --NHR⁴, and --N(R⁴)₂ ;M is a cation selected from the group consisting of Na+, K+, Mg++, Ca++,Zn++, NH₄ +, alkylammonium, dialkylammonium, trialkylammonium, andtetralkylammonium; each R⁴ is independently selected from the groupconsisting of H, C₁ -C₈ straight or branched chain alkyl,N,N-dimethylaminoethyl, 2-hydroxyethyl, 2-methoxyethyl, and2-ethoxyethyl; and R⁵ and R⁶ are independently selected from the groupconsisting of H, C₁ -C₈ straight or branched chain alkyl, methoxy,ethoxy, 2-hydroxyethoxy, 2-methoxyethyl, and 2-ethoxyethyl.

Representative nonlimiting examples of monomers useful herein includeacrylic acid and salts, esters, and amides thereof. The salts can bederived from any of the common nontoxic metal, ammonium, or substitutedammonium counter ions. The esters can be derived from C₁₋₄₀ straightchain, C3-40 branched chain, or C3-40 carbocyclic alcohols; frompolyhydric alcohols having from about 2 to about 8 carbon atoms and fromabout 2 to about 8 hydroxy groups (nonlimiting examples of which includeethylene glycol, propylene glycol, butylene glycol, hexylene glycol,glycerin, and 1,2,6-hexanetriol); from amino alcohols (nonlimitingexamples of which include aminoethanol, dimethylaminoethanol, anddiethylaminoethanol, and their quaternized derivatives); or from alcoholethers (nonlimiting examples of which include methoxyethanol, and ethoxyethanol). The amides can be unsubstituted, N-alkyl or N-alkylaminomono-substituted, or N,N-dialkyl or N,N-dialkylamino di-substituted,wherein the alkyl or alkylamino group can be derived from C₁₋₄₀ straightchain, C3-40 branched chain, or C3-40 carbocylic moieties. Additionally,the alkylamino groups can be quaternized. Also useful as monomers aresubstituted acrylic acids and salts, esters, and amides thereof (whereinthe substituents are on the two and three carbon positions of theacrylic acid and are independently selected from the group consisting ofC₁₋₄ alkyl, --CN, --COOH (e.g., methacrylic acid, ethacrylic acid, and3-cyano acrylic acid). The salts, esters, and amides of thesesubstituted acrylic acids can be defined as described above for theacrylic acid salts, esters, and amides. Other useful monomers includevinyl and allyl esters of C₁₋₄₀ straight chain, C3-40 branched chain, orC3-40 carbocylic carboxylic acids; vinyl and allyl halides (e.g., vinylchloride and allyl chloride); vinyl and allyl substituted heterocyliccompounds (e.g., vinyl pyrridine and allyl pyridine); vinylidenechloride; and hydrocarbons having at least one carbon-carbon double bond(e.g., styrene, alpha-methylstyrene, t-butylstyrene, butadiene,isoprene, cyclohexadiene, ethylene, propylene, 1-butene, 2-butene,isobutylene, vinyl toluene); and mixtures thereof.

Preferred A monomers useful herein include those selected from the groupconsisting of acrylic acid, methacrylic acid, ethacrylic acid, methylacrylate, ethyl acrylate, n-butyl acrylate, iso-butyl acrylate, t-butylacrylate, 2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate,ethyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate,t-butyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate,methyl ethacrylate, ethyl ethacrylate, n-butyl ethacrylate, iso-butylethacrylate, t-butyl ethacrylate, 2-ethylhexyl ethacrylate, decylethacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropylmethacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate,hydroxypropyl methacrylate, glyceryl monoacrylate, glycerylmonomethacrylate, acrylamide, methacrylamide, ethacrylamide, N-methylacrylamide, N,N-dimethyl acrylamide, N,N-dimethyl methacrylamide,N-ethylacrylamide, N-isopropyl acrylamide, N-butyl acrylamide, N-t-butylacrylamide, N,N-di-n-butylacrylamide, N,N-diethylacrylamide, N-octylacrylamide, N-octadecyl acrylamide, N-phenyl acrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-dodecylmethacrylamide,N,N-dimethylaminoethyl acrylamide, quaternized N,N-dimethylaminoethylacrylamide, N,N-dimethylaminoethyl methacrylamide, quaternizedN,N-dimethylaminoethyl methacrylamide, N,N-dimethylaminoethyl acrylate,N,N-dimethylamianoethyl methacrylate, quaternized N,N-dimethylaminoethylacrylate, quaternized N,N-dimethylaminoethyl methacrylate,2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethylethacrylate, glyceryl acrylate, 2-methoxyethyl acrylate, 2-methoxyethylmethacrylate, 2-methoxyethyl ethacrylate, 2-ethoxyethyl acrylate,2-ethoxyethyl methacrylate, 2-ethoxyethyl ethacrylate, maleic acid,maleic anhydride and its half esters, crotonic acid, itaconic acid,angelic acid, diallyidimethyl ammonium chloride, vinyl pyrrolidone,methyl vinyl ether, methyl vinyl ketone, maleimide, vinyl pyridine,vinyl imidazole, vinyl furan, styrene sulfonate, allyl alcohol, vinylalcohol, vinyl caprolactam, and mixtures thereof. More preferred Amonomers are those selected from the group consisting of methylacrylate, methyl methacrylate, methyl ethacrylate, ethyl acrylate, ethylmethacrylate, ethyl ethacrylate, n-butyl acrylate, n-butyl methacrylate,n-butyl ethacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate,2-ethylhexyl ethacrylate, N-octyl acrylamide, 2-methoxyethyl acrylate,2-hydroxyethyl acrylate, N,N-dimethylaminoethyl acrylate, and mixturesthereof.

Most preferred A monomers are those selected from the group consistingof n-butyl acrylate, 2-ethylhexyl acrylate, N-octyl acrylamide,2-methoxyethyl acrylate, 2-hydroxyethyl acrylate, N,N-dimethylaminoethylacrylate, and mixtures thereof.

Hydrophilic "B" Macromonomer Units

A macromonomer is a large monomer unit, i.e. a macromolecular monomer,which can be further polymerized with itself, with other conventionalmonomers, or with other macromonomers. The term "macromonomer" is onethat is familiar to the polymer chemist of ordinary skill in the art.The hydrophilic "B" macromonomer units of the present invention are verylarge monomer building blocks which. can be formed from thepolymerization of smaller monomer units. The B macromonomers encompass awide variety of structures and are copolymerizable with the A monomer.Either a single B macromonomer or combinations of two or more Bmacromonomers can be utilized. In either case, the macromonomers areselected to meet the requirements of the copolymer.

The hydrophilic B macromonomers comprise from about 10% to about 60%,more preferably from about 15% to about 50%, and most preferably fromabout 20% to about 40%, by weight of the copolymers.

By the term "copolymerizable" as used herein is meant B macromonomersthat can be reacted with the A monomer in a polymerization reactionusing any conventional synthetic techniques. "Copolymerization" is aterm of art used to refer to the simultaneous polymerization of two ormore different monomers. In the present invention, B macromonomers thatare copolymerizable with A monomers using conventional free radicalinitiated techniques are preferred. By the term "hydrophilic" as usedherein is meant B macromonomers that are soluble in or have an affinityfor water and/or other polar, water-soluble solvent materials (e.g.,methanol, ethanol, propanol, isopropanol and the like). "Hydrophilic" isalso a term of art used to described a substance having a strongtendency to absorb water which results in the swelling, solubilization,or dispersion of the substance in water. Without being limited bytheory, the hydrophilic B macromonomer units are believed to contributeto the overall water or alcohol soluble or dispersible properties of thecopolymers.

B macromonomers that are useful herein contain an ethylenicallyunsaturated moiety that is copolymerizable with the A monomer. The term"ethylenically unsaturated" is used herein to mean B macromonomers thatcontain at least one carbon-carbon double bond (which can be mono-, di-,tri-, or tetra-substituted). Typically, the preferred B macromonomersare those that are endcapped with the ethylenically unsaturated moiety.By "endcapped" as used herein is meant that the ethylenicallyunsaturated moiety is at or near a terminal position of themacromonomer. However, this definition of "endcapped" is not intended tolimit the macromonomer to only those macromonomers which terminate in acarbon-carbon double bond (whether mono-, di-, tri-, ortetra-substituted).

The hydrophilic B macromonomers of the present invention can besynthesized utilizing a variety of standard synthetic proceduresfamiliar to the polymer chemist of ordinary skill in the art.Furthermore, these macromonomers can be synthesized starting fromcommercially available polymers. Typically the weight average molecularweight of the macromonomer is from about 1000 to about 200,000, morepreferably from 1500 to about 30,000, and most preferably from about2000 to about 25,000.

For example, the hydrophilic B macromonomers can be synthesized by thepolymerization (acid, base, free radical, or auto-initiated) of ahydrophilic monomer to form a polymer which is subsequently reacted withor "endcapped" with a structural unit E, containing the ethylenicallyunsaturated moiety. Alternatively, the B macromonomers can besynthesized starting with commercially available hydrophilic polymerswhich are "endcapped" with the structural unit E. In yet anotheralternative, the B macromonomer can be synthesized by starting with thestructural unit E, and polymerizing onto it the desired hydrophilicmonomer units. It is to be understood that in this third alternative,the ethylenically unsaturated moiety of the E unit is not consumed inthe synthesis but its integrity is preserved for subsequentcopolymerization of the B macromonomer with the A monomer units. All ofthe synthetic alternatives are merely illustrative in that any othersuitable synthetic procedures can be utilized to prepare the Bmacromonomers and copolymers of the present invention.

The B macromonomers can be described by the following formula

    [I].sub.n -[X].sub.m -E.

X is a hydrophiljc monomer unit, and m is an integer from about 10 toabout 2000, preferably from about 15 to about 300, and more preferablyfrom about 20 to about 250, so that the macromonomer meets the weightaverage molecular weight requirements set forth above. Preferred is whenX is a hydrophilic monomer unit selected from the group consisting ofoxazolines, N-alkyloxazolines, alkylene glycols, N-vinylpyrrolidones,N-allylpyrrolidones, vinylpyridines, allylpyridiens, vinylcaprolactams,allylcaprolactams, vinylimidazoles, allylimidaoles, vinylfurans,allylfurans, vinyltetrahydrofurans, allyltetrahydrofurans,vinaylaminobenzenes, vinylaminomethylbenzenes, vinylaminoethylbenzenes,N,N-dialkylacrylamides, N,N-dialkyl(alkyl)acrylamides, and mixturesthereof. More preferred is wherein X is a monomer unit selected from thegroup consisting of N-alkyloxazolines, alkylene glycols, vinylpyridines,N,N-dialkylacrylamides, N,N-dialkyl(alkyl)acrylamides, and mixturesthereof. Most preferred is wherein X is a monomer unit selected fromvinylpyridines.

E is a structural unit containing the ethylenically unsaturated moietyor "endcapping" group. Preferred is when E is selected from the groupconsisting of vinyl, allyl, acryloyl, methacryloyl, ethacryloyl, styryl,3-vinylbenzyl, 4-vinylbenzyl, 3-vinylbenzoyl, 4-vinylbenzoyl, 1-butenyl,1-propenyl, isobutenyl, isoprenyl, cyclohexyl, cylcopentyl, and mixturesthereof. More preferred is when E is selected from the group consistingof vinyl, allyl, acryloyl, methacryloyl, ethacryloyl, 3-vinylbenzyl,4-vinylbenzyl, 3-vinylbenzoyl, 4-vinylbenzoyl, 1-butenyl, 1-propenyl,isobutenyl, and mixtures thereof. Most preferred is when E is selectedfrom the group consisting of vinyl, allyl, acryloyl, methacryloyl,ethacryloyl, 3-vinylbenzyl, 4-vinylbenzyl, and mixtures thereof.

I is an optionally present chemical moiety. In other words, n is aninteger selected from zero and one. Without being limited by theory, Ican be derived from a chemical initiator or solvent used in thesynthesis of the B macromonomer. Nonlimiting examples of such initiatorsfrom which I can be derived include hydrogen ion, hydrogen radical,hydride ion, hydroxide ion, hydroxyl radical, peroxide radical, peroxideanion, C1-20 carbocations, C1-20 carbanions, C1-20 carbon radicals,C1-20 aliphatic and aromatic alkoxy anions, ammonium ion, andsubstituted ammonium ions (e.g., C1-20 alkyl and C1-20 alkoxysubstituted). I can be derived from any useful solvent, nonlimitingexamples of which inicude water, methanol ethanol, propanol,isopropanol, acetone, hexane, dichloromethane, chloroform, benzene, andtoluene. Nonlimiting examples of I include chemical moieties selectedfrom the group consisting of H, C1-C6 alkyl, phenyl, 4-methylphenyl, andbenzyl; preferably H, methyl, ethyl, and phenyl; and more preferably H,methyl, and ethyl.

Representative examples of classes of endcapped B macromonomers usefulherein include those selected from the group consisting of endcappedpoly(N-alkyloxazolines), endcapped polyalkylene glycols, endcappedpolyalkylene glycol monoalkyl ethers, endcappedpoly(N-vinylpyrrolidones), endcapped poly(N-allylpyrrolidones),endcapped polyvinylpyridines, endcapped polyallylpyridines, endcappedpolyvinylcaprolactams, endcapped polyallylcaprolactams, endcappedpolyvinylimidazoles, endcappped polyallylimidazoles, endcappedpolyvinylfurans, endcapped polyvinyltetrahydrofurans, endcappedpolyallylfurans, endcapped polyacrylic acids, endcapped polymethacrylicacids, endcapped polyallyltetrahdyrofurans, endcappedpolyvinylaminobenzenes, endcapped polyvinyl (N,N-dialkylaminobenzenes),endcapped polyvinyl (N-alkylaminobenznes), endcappedpolyvinylaminomethylbenzenes, endcapped polyvinyl(N,N-dialkylaminomethylbenzenes), endcapped polyvinyl(N,alkylaminomethylbenzenes), endcapped polyvinylaminoethylbenzenes,endcapped polyvinyl (N,N-dialkylaminoethylbenzenes), endcapped polyvinyl(N-alkylaminoethylbenenes), endcapped poly(N,N-dialkylacrylamides),endcapped poly(N,N-dialkyl(alkyl)acrylamides), and mixtures thereof.

Preferred are macromonomers selected from the group consisting ofendcapped poly(N-alkyloxazolines), endcapped polyalkylene glycols,endcapped polyalkylene glycol monoalkyl ethers, endcappedpolyvinylpyridines, endcapped polyacrylamides, and mixtures thereof.

More preferred are endcapped polyvinylpyridine and endcappedpolyacrylamide macromonomers.

Examples of endcapped poly(N-alkyloxazoline) macromonomers are thosehaving the following chemical formula: ##STR8## wherein R and R' areindependently selected from H or C₁₋₈ straight or branched chain alkyl,more preferably R and R' are independently selected from H, methyl, orethyl; and most preferably R is methyl and R' is ethyl. E is acopolymerizable, ethylenically unsaturated moiety (i.e. the endcappingmoiety). Preferred is when E is selected from the group consisting ofvinyl, allyl, acryloyl, methacryloyl, ethacryloyl, styryl,3-vinylbenzyl, 4-vinylbenzyl, 3-vinylbenzoyl, 4-vinylbenzoyl, 1-butenyl,1-propenyl, isobutenyl, isoprenyl, cyclohexyl, cylcopentyl, and mixturesthereof. More preferred is when E is selected from the group consistingof vinyl, allyl, acryloyl, methacryloyl, ethacryloyl, 3-vinylbenzyl,4-vinylbenzyl, 3-vinylbenzoyl, 4-vinylbenzoyl, 1-butenyl, 1-propenyl,isobutenyl, and mixtures thereof. Most preferred is when E is selectedfrom the group consisting of vinyl, allyl, acryloyl, methacryloyl,ethacryloyl, styryl, 3-vinylbenzyl, 4-vinylbenzyl, and mixtures thereof.In the above structure m is preferably an integer from about 10 to about2000, more preferably from about 15 to about 300, and most preferablyfrom about 20 to about 250. Alternatively, other examples of endcappedpoly(N-alkyloxazoline) macromonomers are those having the followingchemical formula: ##STR9## wherein R and R' are independently selectedfrom the group consisting of H or C₁₋₈ straight or branched chain alkyl,more preferably R and R' are independently selected from H, methyl, orethyl; and most preferably R is H and R' is ethyl. In the abovestructure m is an integer from about 10 to about 2000, more preferablyfrom about 15 to about 300, and most preferably from about 20 to about250. Highly preferred examples of endcapped poly(N-alkyloxazoline)macromonomers useful herein include acryloyl endcapped poly(2-ethyloxazoline), methacryloyl endcapped poly(2-ethyl oxazoline), styrylendcapped poly(2-ethyloxazoline), acryloyl endcapped poly(2-methyloxazoline), methacryloyl endcapped poly(2-methyl oxazoline),3-vinylbenzoyl endcapped poly(2-methyloxazoline), 4-vinylbenzoylendcapped poly(2-methyloxazoline), and mixtures thereof.

The endcapped poly(N-alkyloxazoline) macromonomers can be synthesizedusing standard synthetic procedures which involve polymerizing, usuallyunder acid-catalyzed conditions, an N-alkyloxazoline to yield apoly(N-alkyloxazoline) alcohol. This alcohol can then be subsequentlyendcapped, employing standard reaction procedures, with the desiredethylenically unsaturated moiety using a reactive or activated form ofan endcapping group. Suitable activated endcapping groups include vinyl,allyl, 1-propenyl, 3-vinylbenzyl, 4-vinylbenzyl, 3-vinylbenzoyl, and4-vinylbenzoyl halides (e.g. chlorides, bromides, and iodides), and theacid chlorides and bromides derived from acrylic acid, methacrylic acid,and ethacrylic acid. See, e.g., S. I. Shoda et al., "Synthesis andSurfactant Property of Copolymers Having a Poly(2-Oxazoline) GraftChain", Journal of Polymer Science: Part A: Polymer Chemistry, vol. 30,pp. 1489-1494 (1992); T. Saegusa et al., "Macromolecular Engineering onthe Basis of the Polymerization of 2-Oxazolines, Makromol. Chem.,Macromol. Symp., vol. 51, pp. 1-10 (1991); S. Kobayashi et al.,Macromolecules, vol 22, pp. 2878-2884 (1989), and U.S. Pat. No.4,011,376, to Tomalia et al., issued Mar. 8, 1977; and U.S. Pat. No.3,786,116, to Milkovich et al., issued Jan. 15, 1974; all of which areincorporated herein by reference.

Alternatively the polyoxazoline macromonomers can be synthesized bypolymerizing the monomers onto an appropriate endcapping group. Forexample, the vinyl benzyl endcapped polyoxazolines can be prepared bypolymerizing 2-ethyl-2-oxazoline onto a mixture of 3-vinylbenzyl and4-benzylchlorides. See EXAMPLE III.

Also highly useful herein are endcapped polyalkylene glycol monoalkylether macromonomers corresponding to the following general chemicalformula ##STR10## wherein R" is selected from C1-C40 straight orbranched chain alkyl, more preferably from C1-C8 straight or branchedchain alkyl, most preferably from C1-C4 straight or branched chainalkyl, and most preferably methyl; R³ is selected from hydrogen, methyl,ethyl, or n-propyl, more preferably from hydrogen or methyl, mostpreferably from H. E is a copolymerizable, ethylenically unsaturatedmoiety (i.e. the endcapping moiety). Preferred is when E is selectedfrom the group consisting of vinyl, allyl, acryloyl, methacryloyl,ethacryloyl, styryl, 3-vinylbenzyl, 4-vinylbenzyl, 3-vinylbenzoyl,4-vinylbenzoyl, 1-butenyl, 1-propenyl, isobutenyl, isoprenyl,cyclohexyl, cylcopentyl, and mixtures thereof. More preferred is when Eis selected from the group consisting of vinyl, allyl, acryloyl,methacryloyl, ethacryloyl, 3-vinylbenzyl, 4-vinylbenzyl, 3-vinylbenzoyl,4-vinylbenzoyl, 1-butenyl, 1-propenyl, isobutenyl, and mixtures thereof.Most preferred is when E is selected from the group consisting of vinyl,allyl, acryloyl, methacryloyl, ethacryloyl, styryl, 3-vinylbenzyl,4-vinylbenzyl, and mixtures thereof. In the above structure, m is asdescribed previously, wherein m is preferably an integer from about 20to about 2000, more preferably from about 30 to about 750, and mostpreferably from about 40 to about 500. It is to be understood that inthe above structure, that when R³ is other than hydrogen that variousisomers of the resulting macromonomer are possible depending upon theorientation of the individual glycol moieties. Therefore, the structuredepicted above for these endcapped polyalkylene glycol monolkayl ethersis a general one that is not intended to limit these materials to anyone particular isomeric structure.

Highly preferred examples of endcapped polyalkylene glycol monoalkylethers useful herein inlcude acryloyl endcapped polyethylene glycolmonomethyl ether, 3-vinylbenzoyl endcapped polyethylene glycolmonomethyl ether, 4-vinylbenzoyl endcapped polyethylene glycolmonomethyl ether, methacryloyl endcapped polyethylene glycol monomethylether, and mixtures thereof.

The endcapped polyalkylene glycol monoalkyl ethers can be synthesizedfrom the polyalkylene glycol monoalkyl ether and the reactive oractivated form of an endcapping group employing standard reactionprocedures. Suitable activated endcapping groups include vinyl, allyl,3-vinylbenzoyl, and 4-vinylbenzoyl halides (e.g. chlorides, bromides,and iodides), and the acid chlorides and bromides derived from acrylicacid, methacrylic acid, and ethacrylic acid. The polyalkylene glycolmonoalkyl ether can be synthesized from the corresponding polyalkyleneglycol using any of the alkylating agents well known in the art (e.g.,methyl iodide, methyl bromide, diazomethane, methyl sulfate, ethyliodide). Polyethylene glycols of various molecular weight ranges, aswell as their methyl ethers are commercially available from AldrichChemical Company and Union Carbide Corporation. Alternatively, thepolyalkylene glycols can be synthesized from the corresponding alkyleneoxides and alkylene glycols using standard synthetic procedures (e.g.,the acid or base catalyzed polymerization of alkylene oxides).

Also highly useful herein are endcapped hydrophilic nitrogen-containingmacromonomer units copolymerizable with A corresponding to the formula##STR11## wherein E is a copolymerizble, ethylenically unsaturatedmoiety (i.e. the endcapping moiety). Preferred is when E is selectedfrom the group consisting of vinyl, allyi, acryloyl, methacryloyl,ethacryloyl, 2-vinyl benzyl 3-vinyl benzyl, 4-vinyl benzyl,2-vinylbenzoyl, 3-vinylbenzoyl, 4-vinylbenzoyl, 1-butenyl, isobutenyl,isoprenyl, cyclopentenyl, cyclohexenyl, and mixtures thereof. Morepreferred is when E is selected from the group consisting of vinyl,allyl, acryloyl, methacryloyl, ethacryloyl, 2-vinylbenzyl,3-vinylbenzyl, 4-vinylbenzyl, 3-vinylbenzoyl, 4-vinylbenzoyl, andmixtures thereof. Most preferred is when E is selected from the groupconsisting of 2-vinylbenzyl, 3-vinylbenzoyl, 4-vinylbenzyl and mixturesthereof. R¹² is selected form the group consisting of hydrogen, C1-6straight or branched chain alkyl, benzyl, 1-phenyl substituted C2-6straight or branched chain alkyl, 1,1-diphenyl substituted C2-6 straightor branched chain alkyl, and mixtures thereof. More preferably R¹² is1,1-diphenyl-4-methylpentyl. P is selected from the group consisting of2-pyridyl, 3-pyridyl, 4-pyridyl, halogen substituted 2-, 3-, or4-pyridyl, C1-4 alkyl substituted 2-, 3-, or 4-pyridyl, 2-aminophenyl,3-aminophenyl, 4-aminophenyl, 2-aminomethylphenyl, 3-aminomethylphenyl,4-aminomethylphenyl, and pharmaceutically acceptable salts andquaternized derivatives thereof, and mixtures thereof. In the precedingstructure, m is preferably an integer from about 10 to about 2000, morepreferably from about 15 to about 300, and most preferably from about 20to about 250.

In the preceding structure it is found that pharmaceutically acceptablesalts and quaternized derivatives are especially preferred because oftheir highly desired physical characteristics and solubilitycharacteristics. By pharmaceutically acceptable salt as used herein ismeant a salt that is generally regarded as safe for human use withoutundue risk of toxicity and other adverse effects. Nonlimiting examplesof pharmaceutically acceptable salts of these materials includehydrochloride salts and hydrobromide salts. Nonlimiting examples ofquaternized derivatives include alkyl quaternized derivatives whereinsaid alkyl group is a C1-30 straight or branched chain moiety,preferably a C1-4 straight or branched chain moiety, more preferablywherein said alkyl group is methyl or ethyl.

Highly preferred examples of these endcapped nitrogen containingmacromonomers useful herein include acryloyl endcapped poly(2-, 3-, or4-vinyl pyridine), acryloyl endcapped poly(2-, 3-, or 4-vinylethylsubstituted pyridine), methacryloyl endcapped poly(2-, 3-, or4-vinyl pyridine), 2-, 3-, or 4-vinyl benzyl edncapped poly(2-, 3-, or4-vinylpyridine), 2-, 3-, or 4-vinyl benzyl endcapped poly(2-, 3-, or4-vinyl pyridine hydrochloride), 2-, 3-, or 4-vinyl benzyl endcappedpoly(2-, 3-l or 4-vinyl methyl-quaternized pyridine), 2-, 3-, or 4-vinylbenzyl endcapped poly(4-dimethylaminomethylvinylbenzene), 2-, 3-, or 4-vinyl benzyl endcapped poly(alkyl-quaternizeddimethylaminoethylvinylbenzene), and mixtures thereof.

These nitrogen containing endcapped macromonomers can be synthesizedusing standard synthetic procedures which involve polymerizing, usuallyunder anionic initiation conditions the appropriate monomer unit, (e.g.2-, 3-, or 4- vinyl pyridine, 4-dimethylaminomethyl vinyl benzene,etc.). A wide variety of initiators can be used, nonlimiting examples ofwhich include bases such as n-butyl lithium, sec-butyl lithium, t-butyllithium, lithium aluminum hydride, sodium hydride, and the like.Nonlimiting examples of these bases are provided in AnionicPolymerization: Principles and Practice, Maurice Morton, Chapter 2, p.13, Academic Press, N.Y. (1983), which is incorporated by referenceherein in its entirety. It has been found especially convenient to usethese strong bases in conjunction with sterically hindered hydrocarbonmaterials such as 1,1-diphenyl ethylene to generate a stericallyhindered base for inititiaing the polymerization reaction, in whichcase, the sterically hindered hydrocarbon is the actual initiator,defined previously as "I", which is incorporated into the macromonomerstructure. Once the desired degree of polymerization is achieved, anappropriate endcapping reagent is typically used to terminate thepolymerization and to endcap the macromonomer, nonlimiting examples ofthese endcapping reagents include 2-vinylbenzyl chloride, 3-vinylbenzylchloride, 4-vinylbenzyl chloride, and the like.

The pharmaceutically acceptable salts and quaternized derivatives ofthese nitorgen containing macromonomers are readily prepared from themacromonomers using standard synthetic procedures. Typically, themacromonomers are reacted with an acid to form the salt. For examplereaction with hydrochloric acid or hydrobromic acid (either gaseous oras an aqueous solution) would yield the corresponding hydrochloride andhydrobromide salts, respectively. To form the quaternized derivativesthe macromoners are reacted with a quaternizing agent. For examplereaction with a methyl halide (e.g., methyl iodide, methyl chloride) oran alkyl sulfate (e.g. dimethyl sulfate, diethylsulfate) would yield thecorresponding quaternized macromonomer.

More typically, the pharmaceutically acceptable salt or quaternizedderivative of the thermoplastic elastomeric polymer is desired, in whichcase the non-salt form or non-quaternized macromonomer is incorporatedinto the thermoplastic elastomeric copolymer, followed by salt formationor quaternization of the copolymer using standard synthetic proceduresanalogous to those described for the macromonomer.

Also highly useful herein are endcapped hydrophilic polyacrylamidemacromonomer units copolymerizable with A corresponding to the formula##STR12## wherein E is a copolymerizable, ethylenically unsaturatedmoiety (i.e. the endcapping moiety). Preferred is when E is selectedfrom the group consisting of vinyl, allyl, acryloyl, methacryloyl,ethacryloyl, 2-vinyl benzyl, 3-vinyl benzyl, 4-vinyl benzyl,2-vinylbenzoyl, 3-vinylbenzoyl, 4-vinylbenzoyl, 1-butentyl, isobutenyl,isoprenyl, cyclohexyl, cyclopententyl, cyclohexenyl, and mixturesthereof. More preferred is when E is selected from the group consistingof vinyl, allyl, acryloyl, methacryloyl, ethacryloyl, 2-vinylbenzyl,3-vinylbenzyl, 4-vinylbenzyl, 3-vinylbenzoyl, 4-vinylbenzoyl, andmixtures thereof. Most preferred is when E is selected from the groupconsisting of 2-vinylbenzyl, 3-vinylbenzyl, 4-vinylbenzyl and mixturesthereof. R¹² is selected from the group consisting of hydrogen, C₁ -C₆straight or branched chain alkyl, benzyl, 1-phenyl substituted C₂₋₆straight or branched chain alkyl, 1,1-diphenyl substituted C₂₋₆ straightor branched chain alkyl, and mixtures thereof.

R¹³ is selected from the group consisting of H and C₁₋₆ straight orbranched chain alkyl, more preferably H and C₁ -C4 straight or branchedchain alkyl, and most preferably H, methyl, and ethyl. R¹⁴, and R¹⁵ areindependently selected from the group consisting of C1-8 straight orbranched chain alkyl; more preferably C1-6 straight or branched chainalkyl, and most preferably methyl. In the preceding structure, m ispreferably an integer from about 10 to about 2000, more preferably fromabout 15 to about 3000, and most preferably from about 20 to about 250.

Polymers of the Present Invention

Particularly preferred polymers for use in the present invention includethe following (the weight percents below refer to the amount ofreactants added in the polymerization reaction, not necessarily theamount in the finished polymer):

N-butyl acrylate/2-methoxyethyl acrylate/Poly(4-dimethylmino methylvinylbenzene) 38/22/40

Methyl quaternized N-butyl acrylate/2-methoxyethylacrylate/poly(4-dimethylaminomethylvinyl benzene) 38/22/40

Ethyl quaternized N-butyl acrylate/2-methoxyethylacrylatelpoly(2-vinylpyridine) 38/22/40

N-butyl acrylate/2-methoxyethyl acrylate/Poly(2-vinylpyridine)hydrochloride 38/22/40

n-butyl acrylate/2-methoxyethyl acrylate/poly(N,N-dimethylacrylamide)38/22/40

n-butyl acrylate/2-methoxyethylacrylate/poly(N,N-dimethylmethacrylamide) 38/22/40

n-butyl acrylate/2-methoxyethyl acrylate/poly(2-ethyl-2-oxazoline)38/22/40

n-butyl acrylate/2-methoxyethyl acrylate/poly(2-ethyl-2-oxazoline)38/22/40

n-butyl acrylate/2-methoxyethyl acrylate/poly(2-ethyl-2-oxazoline)35/25/40

n-butyl acrylate/2-methoxyethyl acrylate/poly(2-ethyl-2-oxazoline)38/22/40

n-butyl acrylate/2-methoxyethyl acrylate/poly(2-ethyl-2-oxazoline)38/22/40

n-butyl acrylate/poly(2-ethyl-2-oxazoline) 60/40

n-butyl acrylate/2-ethylhexyl methacrylate/poly(2-ethyl-2-oxazoline)40/20/40

n-butyl acrylate/2-methoxyethyl acrylate/poly(ethylene glycol) 386/22140

n-butyl acrylate/2-(dimethylamino)ethylmethacrylate/poly(2-ethyl-2-oxazoline) 36/24/40

n-butyl acrylate/methyl quaternized 2-(dimethylamino)ethylmethacrylate/poly(2-ethyl-2-oxazoline) 36/24/40

Synthesis of the Copolymers

In general, the copolymers can be made by free radical polymerization ofthe A monomers with the B macromonomers. It is not intended tonecessarily exclude from this invention any copolymers made by meansother than free radical polymerization, so long as the product has thedesired physical properties. The copolymers herein contain randomlyrepeating monomer units and macromonomer units.

The general principles of free radical polymerization methods are wellunderstood. See, for example, Odian, "Principles of Polymerization", 2ndedition, John Wiley & Sons, 1981, pp. 179-318. The desired monomers andmacromonomers are all placed in a reactor, along with a sufficientamount of a mutual solvent so that when the reaction is complete theviscosity of the reaction is reasonable. Typical monomer andmacromonomer loadings are from about 10% to about 50%, on a weightbasis. Undesired terminators, especially oxygen, can be removed asneeded. This is done by evacuation or by purging with an inert gas, suchas argon or nitrogen. The initiator is introduced and the reactionbrought to the temperature needed for initiation to occur, assumingthermal initiators are used. Nonlimiting examples of suitable initiatorsinclude those selected from the group consisting of azo initiators,peroxide initiators, redox initiators, and photochemical initiators. Thepolymerization is allowed to proceed as long as needed for a high levelof conversion to be achieved, typically from a few hours to a few days.The solvent is then removed, usually by evaporation or by precipitatingthe copolymer by addition of a nonsolvent. The copolymer can be furtherpurified, as needed utilizing a variety of techniques includingfiltration, extraction, trituration, membrane separation, gel permeationchromatography, and like.

There are numerous variations on these procedures which are entirely upto the discretion of the synthetic chemist (e.g., choice of degassingmethod and gas, choice of initiator type, extent of conversion, reactionloading, etc). The choice of initiator and solvent are often determinedby the requirements of the particular monomers and macromonomer used,because different monomers and macromonomers have different solubilitiesand different reactivities to a specific initiator.

The copolymers of the present invention can also be synthesized by firstpresparing the backbone from the polymerization of suitable monomers,followed by further polymerization of the backbone with suitablehydrophilic monomers to form the polymeric side chains. This alternativeprocedure for synthesizing the copolymers herein is illustrated inEXAMPLE VII below.

When salts and/or quaternized polymers are desired, these polymers arereadily prepared from the copolymers using standard procedures, such asreaction with a strong acid or a quaternizing agent. Preferred among theacids are hydrogen chloride and hydrogen bromide, which can be employedeither as a gas or as an aqueous solution. Commonly used quaternizingagents include alkyl halides (e.g., methyl iodide and methyl chloride)and alkyl and dilakyl suflates (e.g., dimethyl sulfate and diethylsulfate).

Analysis of the copolymer reaction product and the extracted materials,and the purified copolymer can be perfomred by conventional analysistechniques known in the art. These include, for example, nuclearmagnetic resource (NMR), infrared molecular spectroscopies, gelpermeation/size exclusion chromatography, membrane osmometry, and atomicabsorption and emission spectroscopies.

Hair Care and Topical Skin Care Compositions

The copolymers of the present invention can be formulated into a widevariety of product types, including mousses, gels, lotions, tonics,sprays, shampoos, conditioners, rinses, hand and body lotions, facialmoisturizers, sunscreens, anti-acne preparations, topical analgesics,mascaras, and the like. The carriers and additional components requiredto formulate such products vary with product type and can be routinelychosen by one skilled in the art. The following is a description of someof these carriers and additional components.

Carriers

Hair Care Compositions

The hair care compositions of the present invention can comprise acarrier, or a mixture of such carriers, which are suitable forapplication to the hair. The carriers are present at from about 0.5% toabout 99.5%, preferably from about 5.0% to about 99.5%, more preferablyfrom about 10.0% to about 98.0%, of the composition. As used herein, thephrase "suitable for application to hair" means that the carrier doesnot damage or negatively affect the aesthetics of hair or causeirritation to the underlying skin.

Carriers suitable for use with hair care compositions of the presentinvention include, for example, those used in the formulation of hairsprays, mousses, tonics, gels, shampoos, conditioners, and rinses. Thechoice of appropriate carrier will also depend on the particularcopolymer to be used, and whether the product formulated is meant to beleft on the surface to which it is applied (e.g., hair spray, mousse,tonic, or gel) or rinsed off after use (e.g., shampoo, conditioner,rinse).

The carriers used herein can include a wide range of componentsconventionally used in hair care compositions. The carriers can containa solvent to dissolve or disperse the particular copolymer being used,with water, the C1-C6 alcohols, and mixtures thereof being preferred;and water, methanol, ethanol, isopropanol, and mixtures thereof beingmore preferred. The carriers can also contain a wide variety ofadditional materials inlcuding, but not limited to acetone, hydrocarbons(such as isobutane, hexane, decene), halogenated hydrocarbons (such asFreons), linalool, esters (such as ethyl acetate, dibutyl phthalate),and volatile silicon derivatives (especially siloxanes such as phenylpentamethyl disiloxane, methoxypropyl heptamethyl cyclotetrasiloxane,chloropropyl pentamethyl disiloxane, hydroxypropyl pentamethyldisiloxane, octamethyl cyclotetrasiloxane, decamethylcyclopentasiloxane, cyclomethicone, and dimethicone having for example,a viscosity at 25° C. of about 15 centipoise or less), and mixturesthereof. When the hair care composition is a hair spray, tonic, gel, ormousse the preferred solvents include water, ethanol, volatile siliconederivatives, and mixtures thereof. The solvents used in such mixturesmay be miscible or immiscible with each other. Mousses and aerosol hairsprays can also utilize any of the conventional propellants to deliverthe material as a foam (in the case of a mousse) or as a fine, uniformspray (in the case of an aerosol hair spray). Examples of suitablepropellants include materials such as trichlorofluoromethane,dichlorodifluoromethane, difluoroethane, dimethylether, propane,n-butane or isobutane. A tonic or hair spray product having a lowviscosity may also utilize an emulsifying agent. Examples of suitableemulsifying agents include nonionic, cationic, anionic surfactants, ormixtures thereof. Fluorosurfactants are especially preferred,particularly if the product is a hair spray composition and mostespecially if it is a spray composition having relatively low levels ofvolatile organic solvents, such as alcohols, and relatively high levelsof water (e.g., in excess of about 10%, by weight water). If such anemulsifying agent is used, it is preferably present at a level of fromabout 0.01% to about 7.5% of the composition. The level of propellantcan be adjusted as desired but is generally from about 3% to about 30%of mousse compositions and from about 15% to about 50% of the aerosolhair spray compositions.

Suitable spray containers are well known in the art and includeconventional, non-aerosol pump sprays i.e., "atomizers," aerosolcontainers or cans having propellant, as described above, and also pumpaerosol containers utilizing compressed air as the propellent. Pumpaerosol containers are disclosed, for example, in U.S. Pat. Nos.4,077,441, Mar. 7, 1978, Olofsson and 4,850,577, Jul. 25, 1989,TerStege, both incorporated by reference herein, and also in U.S. Ser.No. 071839,648, Gosselin, Lund, Sojka, and Lefebvre, filed Feb. 21,1992, "Consumer Product Package Incorporating A Spray Device UtilizingLarge Diameter Bubbles. Pump aerosols hair sprays using compressed airare also currently marketed by The Procter & Gamble Company under theirtradename VIDAL SASSOON AIRSPRAYR hair sprays.

Where the hair care compositions are conditioners and rinses the carriercan include a wide variety of conditioning materials. Where the haircare compositions are shampoos, the carrier can include surfactants,suspending agents, thickeners etc. Various additional components usefulin hair care compositions are described in U.S. Pat. No. 5,106,609, toBolich, Jr. et al., issued Apr. 21, 1992; and U.S. Pat. No. 4,387,090,to Bolich, Jr. issued Jun. 7, 1983; which are incorporated by referenceherein. Some of these additional components are described below.

Topical Skin Care Compositions

The topical cosmetic and pharmaceutical compositions of the presentinvention can comprise a carrier. The carrier should be "cosmeticallyand/or pharmaceutically acceptable", which means that the carrier issuitable for topical application to the skin, has good aestheticproperties, is compatible with the copolymers of the present inventionand any other components, and will not cause any untoward safety ortoxicity concerns.

The carrier can be in a wide variety of forms. For example, emulsioncarriers, including, but not limited to, oil-in-water, water-in-oil,water-in-oil-in-water, and oil-in-water-in-silicone emulsions, areuseful herein. These emulsions can cover a broad range of viscosities,e.g, from about 100 cps to about 200,000 cps. These emulsions can alsobe delivered in the form of sprays using either mechanical pumpcontainers or pressurized aerosol containers using conventionalpropellants. These carriers can also be delivered in the form of amousse. Other suitable topical carriers include anhydrous liquidsolvents such as oils, alcohols, and silicones (e.g., mineral oil,ethanol, isopropanol, dimethicone, cyclomethicone, and the like);aqueous-based single phase liquid solvents (e.g., hydro-alcoholicsolvent systems); and thickened versions of these anhydrous andaqueous-based single phase solvents (e.g., where the viscosity of thesolvent has been increased to form a solid or semi-solid by the additionof appropriate gums, resins, waxes, polymers, salts, and the like).Examples of topical carrier systems useful in the present invention aredescribed in the following four references all of which are incorporatedherein by reference in their entirety: "Sun Products Formulary"Cosmetics & Toiletries, vol. 105, pp. 122-139 (December 1990); "SunProducts Formulary", Cosmetics & Toiletries, vol. 102, pp. 117-136(March 1987); U.S. Pat. No. 4,960,764 to Figueroa et al., issued Oct. 2,1990; and U.S. Pat. No. 4,254,105 to Fukuda et al., issued Mar. 3, 1981.

The carriers of the skin care compositions can comprise from about 50%to about 99% by weight of the compositions of the present invention,preferably from about 75% to about 99%, and most preferably from about85% to about 95%.

Preferred cosmetically and/or pharmaceutically acceptable topicalcarriers include hydro-alcoholic systems and oil-in-water emulsions.When the carrier is a hydro-alcoholic system, the carrier can comprisefrom about 1% to about 99% of ethanol, isopropanol, or mixtures thereof,and from about 1% to about 99% of water. More preferred is a carriercomprising from about 5% to about 60% of ethanol, isopropanol, ormixtures thereof, and from about 40% to about 95% of water. Especiallypreferred is a carrier comprising from about 20% to about 50% ofethanol, isopropanol, or mixtures thereof, and from about 50% to about80% of water. When the carrier is an oil-in-water emulsion, the carriercan include any of the common excipient ingredients for preparing theseemulsions. Additional components useful in formulating these topicalcompositions are further described below.

Additional Components

A wide variety of additional components can be employed in the hair careand topical skin compositions herein. Non-limiting examples include thefollowing:

Pharmaceutical Actives

The compositions of the present invention, especially the topical skincare compositions, can comprise a safe and effective amount of apharmaceutical active. The phrase "safe and effective amount", as usedherein, means an amount of an active high enough to significantly orpositively modify the condition to be treated, but low enough to avoidserious side effects (at a reasonable benefit/risk ratio), within thescope of sound medical judgement. A safe and effective amount of thepharmaceutical active will vary with the specific active, the ability ofthe composition to penetrate the active through the skin, the amount ofcomposition to be applied, the particular condition being treated, theage and physical condition of the patient being treated, the severity ofthe condition, the duration of the treatment, the nature of concurrenttherapy, and like factors.

The pharmaceutical actives which can be used in the compositions of thepresent invention preferably comprise from about 0.1% to about 20% byweight of the compositions, more preferably from about 0.1% to about10%, and most preferably from about 0.1% to about 5%. Mixtures ofpharmaceutical actives may also be used.

Nonlimiting examples of pharmaceutical actives can include thefollowing:

Useful pharmaceutical actives in the compositions of the presentinvention include anti-acne drugs. Anti-acne drugs preferred for use inthe present invention include the keratolytics such as salicylic acid,sulfur, lactic acid, glycolic, pyruvic acid, urea, resorcinol, andN-acetylcysteine; retinoids such as retinoic acid and its derivatives(e.g., cis and trans); antibiotics and antimicrobials such as benzoylperoxide, octopirox, erythromycin, zinc, tetracyclin, triclosan, azelaicacid and its derivatives, phenoxy ethanol and phenoxy proponol,ethylacetate, clindamycin and meclocycline; sebostats such asflavinoids; alpha and beta hydroxy acids; and bile salts such as scymnolsulfate and its derivatives, deoxycholate, and cholate. Preferred foruse herein is salicylic acid.

Useful pharmacetuical actives in the compositions of the presentinvention include non-steroidal anti-inflammatory drugs (NSAIDS). TheNSAIDS can be selected from the following categories: propionic acidderivatives; acetic acid derivatives; fenamic acid derivatives;biphenylcarboxylic acid derivatives; and oxicams. All of these NSAIDSare fully described in the U.S. Pat. No. 4,985,459 to Sunshine et al.,issued Jan. 15, 1991, incorporated by reference herein. Most preferredare the propionic NSAIDS including but not limited to aspirin,acetaminophen, ibuprofen, naproxen, benoxaprofen, flurbiprofen,fenoprofen, fenbufen, ketoprofen, indoprofen, pirprofen, carprofen,oxaprozin, pranoprofen, miroprofen, tioxaprofen, suprofen, alminoprofen,tiaprofenic acid, fluprofen and bucloxic acid. Also useful are thesteroidal anti-inflammatory drugs including hydrocortisone and the like.

Useful pharmaceutical actives in the compositions of the presentinvention include antipruritic drugs. Antipruritic drugs preferred forinclusion in compositions of the present invention includepharmaceutically-acceptable salts of methdilizine and trimeprazine.Useful pharmaceutical actives in the compositions of the presentinvention include include anesthetic drugs. Anesthetic drugs preferredfor inclusion in compositions of the present invention includepharmaceutically-acceptable salts of lidocaine, bupivacaine,chlorprocaine, dibucaine, etidocaine, mepivacaine, tetracaine,dyclonine, hexylcaine, procaine, cocaine, ketamine, pramoxine andphenol. Useful pharmaceutical actives in the compositions of the presentinvention include antimicrobial drugs (antibacterial, antifungal,antiprotozoal and antiviral drugs). Antimicrobial drugs preferred forinclusion in compositions of the present invention includepharmaceutically-acceptable salts of b-lactam drugs, quinolone drugs,ciprofloxacin, norfloxacin, tetracycline, erythromycin, amikacin,triclosan, doxycycline, capreomycin, chlorhexidine, chlortetracycline,oxytetracycline, clindamycin, ethambutol, metronidazole, pentamidine,gentamicin, kanamycin, lineomycin, methacycline, methenamine,minocycline, neomycin, netilmicin, paromomycin, streptomycin,tobramycin, miconazole and amanfadine. Antimicrobial drugs preferred forinclusion in compositions of the present invention include tetracyclinehydrochloride, erythromycin estolate, erythromycin stearate (salt),amikacin sulfate, doxycycline hydrochloride, capreomycin sulfate,chlorhexidine gluconate, chlorhexidine hydrochloride, chlortetracyclinehydrochloride, oxytetracycline hydrochloride, clindamycin hydrochloride,ethambutol hydrochloride, metronidazole hydrochloride, pentamidinehydrochloride, gentamicin sulfate, kanamycin sulfate, lineomycinhydrochloride, methacycline hydrochloride, methenamine hippurate,methenamine mandelate, minocycline hydrochloride, neomycin sulfate,netilmicin sulfate, paromomycin sulfate, streptomycin sulfate,tobramycin sulfate, miconazole hydrochloride, amanfadine hydrochloride,amanfadine sulfate, triclosan, octopirox, parachlorometa xylenol,nystatin, tolnaftate and clotrimazole.

Also useful herein are sunscreening agents. A wide variety ofsunscreening agents are described in U.S. Pat. No. 5,087,445, to Haffeyet al., issued Feb. 11, 1992; U.S. Pat. No. 5,073,372, to Turner et al.,issued Dec. 17, 1991; U.S. Pat. No. 5,073,371, to Turner et al. issuedDec. 17, 1991; and Segarin, et al., at Chapter VIII, pages 189 et seq.,of Cosmetics Science and Technology, all of which are incorporatedherein by reference in their entirety. Preferred among those sunscreenswhich are useful in the compositions of the instant invention are thoseselected from the group consisting of 2-ethylhexyl p-methoxycinnamate,2-ethylhexyl N,N-dimethyl-p-aminobenzoate, p-aminobenzoic acid,2-phenylbenzimidazole-5-sulfonic acid, octocrylene, oxybenzone,homomenthyl salicylate, octyl salicylate,4,4'-methoxy-t-butyidibenzoylmethane, 4-isopropyl dibenzoylmethane,3-benzylidene camphor, 3-(4-methylbenzylidene) camphor, titaniumdioxide, zinc oxide, silica, iron oxide, and mixtures thereof.

Still other useful sunscreens are those disclosed in U.S. Pat. No.4,937,370, to Sabatelli, issued Jun. 26, 1990; and U.S. Pat. No.4,999,186, to Sabatelli et al., issued Mar. 12, 1991; these tworeferences are incorporated by reference herein in their entirety. Thesunscreening agents disclosed therein have, in a single molecule, twodistinct chromophore moieties which exhibit different ultra-violetradiation absorption spectra. One of the chromophore moieties absorbspredominantly in the UVB radiation range and the other absorbs stronglyin the UVA radiation range. These sunscreening agents provide higherefficacy, broader UV absorption, lower skin penetration and longerlasting efficacy relative to conventional sunscreens. Especiallypreferred examples of these sunscreens include those selected from thegroup consisting of 4-N,N-(2-ethylhexyl)methylaminobenzoic acid ester of2,4-dihydroxybenzophenone, 4-N,N-(2-ethylhexyl)methylaminobenzoic acidester with 4-hydroxydibenzoylmethane,4-N,N-(2ethylhexyl)methylaminobenzoic acid ester of2-hydroxy4-(2-hydroxyethoxy)benzophenone,4-N,N-(2-ethylhexyl)-methylaminobenzoic acid ester of4-(2-hydroxyethoxy)dibenzoylmethane, and mixtures thereof.

Generally, the sunscreens can comprise from about 0.5% to about 20% ofthe compositions useful herein. Exact amounts will vary depending uponthe sunscreen chosen and the desired Sun Protection Factor (SPF). SPF isa commonly used measure of photoprotection of a sunscreen againsterythema. See Federal Register, Vol. 43, No. 166, pp. 38206-38269, Aug.25, 1978, which is incorporated herein by reference in its entirety.

Also useful in the present invention are sunless tanning agentsincluding dihydroxyacetone, glyceraldehyde, indoles and theirderivatives, and the like. These sunless tanning agents may also be usedin combination with the sunscreen agents.

Other useful actives include skin bleaching (or lightening) agentsincluding but not limited to hydroquinone, ascorbic acid, kojic acid andsodium metabisulfite.

Other useful actives which are especially useful for hair carecompositions include anti-dandruff actives such as zinc pyrithione,octopirox, selenium disulfide, sulfur, coal tar, and the like.

Conditioners

Conditioning agents useful herein, and especially useful for hair carecompositions, include hydrocarbons, silicone fluids, and cationicmaterials.

The hydrocarbons can be either straight or branched chain and cancontain from about 10 to about 16, preferably from about 12 to about 16carbon atoms. Examples of suitable hydrocarbons are decane, dodecane,tetradecane, tridecane, and mixtures thereof.

Silicone conditioning agents useful herein can include either cyclic orlinear polydimethylsiloxanes, pheny and alkyl phenyl silicones, andsilicone copolyols. The linear volatile silicones generally haveviscosities of less than about 5 centistokes at 25° C., while the cylicmaterials have viscosities less than about 10 centistokes.

Cationic conditioning agents useful herein can include quaternaryammonium salts or the salts of fatty amines. Preferred quaternaryammonium salts are dialkyl dimethyl ammonium chlorides, wherein thealkyl groups have from 12 to 22 carbon atoms and are derived fromlong-chain fatty acids. Representative examples of quaternary ammoniumsalts include ditallow dimethyl ammonium chloride, ditallow dimethylammonium methyl sulfate, dihexadecyl dimethyl ammonium chloride, anddi(hydrogenated tallow) ammonium chloride. Other qauternary ammoniumsalts useful herein are dicationics such as tallow propane diammoniumdichloride. Quaternary imidazolinium salts are also useful herein.Examples of such materials are those imidazolinium salts containingC12-22 alkyl groups such as1-methyl-1-[(stearoylamide)ethyl]-2-heptadecyl-4, 5-dihydroimidazoliniumchloride,1-methyl-1-[(palmitoylamide)ethyl]-2-octadecyl-4,5-dihydroimidazoliniumchloride and 1-methyl-1-[(tallowamide)-ethyl]-2-tallow-imidazoliniummethyl sulfate. Also useful herein are salts of fatty amines. Examplesof such compounds include stearylamine hydrochloride, soyaminehydrochloride, and stearylamine formate. Useful conditioning agents aredisclosed in U.S. Pat. No. 4,387,090, to Bolich, issued Jun. 7, 1983,which is incorporated by reference herein.

Humectants and Moisturizers

The compositions of the present invention can contain one or morehumectant or moisturizing materials. A variety of these materials can beemployed and each can be present at a level of from about 0.1% to about20%, more preferably from about 1% to about 10% and most preferably fromabout 2% to about 5%. These materials include urea; guanidine; glycolicacid and glycolate salts (e.g. ammonium and quaternary alkyl ammonium);lactic acid and lactate salts (e.g. ammonium and quaternary alkylammonium); aloe vera in any of its variety of forms (e.g., aloe veragel); polyhydroxy alcohols such as sorbitol, glycerol, hexanetriol,propylene glycol, butylene glycol, hexylene glycol and the like;polyethylene glycols; sugars and starches; sugar and starch derivatives(e.g., alkoxylated glucose); hyaluronic acid; lactamidemonoethanolamine; acetamide monoethanolamine; and mixtures thereof.Preferred humectants and moisturizers are glycerol, butylene glycol,hexylene glycol, and mixtures thereof.

Surfactants

The compositions of the present invention, especially the shampoo andconditioner compositions, can contain one or more surfactants. Thesesurfactants are useful adjuncts for the carriers of the presentcompositions, and are not required for solubilizing or dispersing thecopolymers of the present invention. For a shampoo, the level ispreferably from about 10% to about 30%, preferably from 12% to about25%, of the composition. For conditioners, the preferred level ofsurfactant is from about 0.2% to about 3%. Surfactants useful incompositions of the present invention include anionic, nonionic,cationic, zwitterionic and amphoteric surfactants. A wide variety ofsurfactants useful herein are disclosed in U.S. Pat. No. 5,151,209, toMc Call et al., issued Sep. 29, 1992; U.S. Pat. No. 5,151,210, to Steuriet al., issued Sep. 29, 1992; and U.S. Pat. No. 5,120,532, to Wells etal., issued Jun. 9, 1992, all of which are incorporated by referenceherein.

Nonlimiting examples of these surfactants include anionic surfactantssuch as alkyl and alkyl ether sulfates. These materials typically havethe respective formulae ROSO₃ M and RO(C₂ H₄ O)_(x) SO₃ M, wherein R isalkyl or alkenyl of from about 10 to about 20 carbon atoms, x is 1 to10, and M is a water-soluble cation such as ammonium, sodium, potassiumand triethanolamine. Another suitable class of anionic surfactants arethe water-soluble salts of the organic, sulfuric acid reaction productsof the general formula:

    R.sub.1 --SO.sub.3 --M

wherein R₁ is chosen from the group consisting of a straight or branchedchain, saturated aliphatic hydrocarbon radical having from about 8 toabout 24, preferably about 12 to about 18, carbon atoms; and M is acation. Additional examples of anionic synthetic surfactants which comewithin the terms of the present invention are the reaction products offatty acids esterified with isethionic acid and neutralized with sodiumhydroxide where, for example, the fatty acids are derived from coconutoil; sodium or potassium salts of fatty acid amides of methyl tauride inwhich the fatty acids, for example, are derived from coconut oil. Stillother anionic synthetic surfactants include the class designated assuccinamates, olefin sulfonates having about 12 to about 24 carbonatoms, and b-alkyloxy alkane sulfonates. Many additional nonsoapsynthetic anionic surfactants are described in McCutcheon's, Detergentsand Emulsifiers, 1984 Annual, published by Allured PublishingCorporation, which is incorporated herein by reference. Also U.S. Pat.No. 3,929,678, Laughlin et al., issued Dec. 30, 1975, discloses manyother anionic as well as other surfactant types and is incorporatedherein by reference.

Nonionic surfactants useful herein are preferably used in combinationwith an anionic, amphoteric or zwitterionic surfactant. These nonionicsurfactants can be broadly defined as compounds produced by thecondensation of alkylene oxide groups (hydrophilic in nature) with anorganic hydrophobic compound, which may be aliphatic or alkyl aromaticin nature.

Cationic surfactants useful in compositions of the present invention aredisclosed in the following documents, all incorporated by referenceherein: M.C. Publishing Co., McCutcheon's, Detergents & Emulsifiers,(North American edition 1979); Schwartz, et al., Surface Active Agents,Their Chemistry and Technology, New York: Interscience Publishers, 1949;U.S. Pat. No. 3,155,591, Hilfer, issued Nov. 3, 1964; U.S. Pat. No.3,929,678, Laughlin, et al., issued Dec. 30, 1975; U.S. Pat. No.3,959,461, Bailey, et al., issued May 25, 1976; and U.S. Pat. No.4,387,090, Bolich, Jr., issued Jun. 7, 1983. If included in thecompositions of the present invention, the cationic surfactant ispresent at from about 0.05% to about 5%.

Zwitterionic surfactants are exemplified by those which can be broadlydescribed as derivatives of aliphatic quaternary ammonium, phosphonium,and sulfonium compounds, in which the aliphatic radicals can be straightor branched chain, and wherein one of the aliphatic substituentscontains from about 8 to about 18 carbon atoms and one contains ananionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate,phosphate, or phosphonate. Other zwitterionics such as betaines are alsouseful in the present invention. Examples of betaines include the highalkyl betaines, such as coco dimethyl carboxymethyl betaine, lauryldimethyl carboxymethyl betaine, lauryl dimethyl alphacarboxyethylbetaine, cetyl dimethyl carboxymethyl betaine, laurylbis-(2-hydroxyethyl) carboxymethyl betaine, stearylbis-(2-hydroxypropyl) carboxymethyl betaine, oleyl dimethyl gammacarboxypropyl betaine, lauryl bis-(2-hydroxypropyl)alpha-carboxyethylbetaine, coco dimethyl sulfopropyl betaine, stearyl dimethyl sulfopropylbetaine, lauryl dimethyl sulfoethyl betaine, lauryl bis-(2-hydroxyethyl)sulfopropyl betaine, and amidobetaines and amidosulfobetaines (whereinthe RCONH(CH₂)₃ radical is attached to the nitrogen atom of thebetaine).

Examples of amphoteric surfactants which can be used in the compositionsof the present invention are those which are broadly described asderivatives of aliphatic secondary and tertiary amines in which thealiphatic radical can be straight or branched chain and wherein one ofthe aliphatic substituents contains from about 8 to about 18 carbonatoms and one contains an anionic water solubilizing group, e.g.,carboxy, sulfonate, sulfate, phosphate, or phosphonate. Examples ofcompounds falling within this definition are sodium3-dodecyl-aminopropionate, sodium 3-dodecylaminopropane sulfonate,N-alkyltaurines such as the one prepared by reacting dodecylamine withsodium isethionate according to the teaching of U.S. Pat. No. 2,658,072,N-higher alkyl aspartic acids such as those produced according to theteaching of U.S. Pat. No. 2,438,091, and the products sold under thetrade name "Miranol" and described in U.S. Pat. No. 2,528,378.

Carboxylic Acid Copolymer Thickeners

Another component useful in the compositions herein is a carboxyliccopolymer thickener. These crosslinked polymers contain one or moremonomers derived from acrylic acid, substituted acrylic acids, and saltsand esters of these acrylic acids and the substituted acrylic acids,wherein the crosslinking agent contains two or more carbon-carbon doublebonds and is derived from a polyhydric alcohol. The preferred polymersfor use herein are of two general types. The first type of polymer is acrosslinked homopolymer of an acrylic acid monomer or derivative thereof(e.g., wherein the acrylic acid has substituents on the two and threecarbon positions independently selected from the group consisting ofC₁₋₄ alkyl, --CN, --COOH, and mixtures thereof). The second type ofpolymer is a crosslinked copolymer having a first monomer selected fromthe group consisting of an acrylic acid monomer or derivative thereof(as just described in the previous sentence), a short chain alcohol(i.e. a C₁₋₄) acrylate ester monomer or derivative thereof (e.g.,wherein the acrylic acid portion of the ester has substituents on thetwo and three carbon positions independently selected from the groupconsisting of C₁₋₄ alkyl, --CN, --COOH, and mixtures thereof), andmixtures thereof; and a second monomer which is a long chain alcohol(i.e. C₈₋₄₀) acrylate ester monomer or derivative thereof (e.g., whereinthe acrylic acid portion of the ester has substituents on the two andthree carbon positions independently selected from the group consistingof C₁₋₄ alkyl, --CN, --COOH, and mixtures thereof). Combinations ofthese two types of polymers are also useful herein.

In the first type of crosslinked homopolymers the monomers arepreferably selected from the group consisting of acrylic acid,methacrylic acid, ethacrylic acid, and mixtures thereof, with acrylicacid being most preferred. In the second type of crosslinked copolymersthe acrylic acid monomer or derivative thereof is preferably selectedfrom the group consisting of acrylic acid, methacrylic acid, ethacrylicacid, and mixtures thereof, with acrylic acid, methacrylic acid, andmixtures thereof being most preferred. The short chain alcohol acrylateester monomer or derivative thereof is preferably selected from thegroup consisting of C₁₋₄ alcohol acrylate esters, C₁₋₄ alcoholmethacrylate esters, C₁₋₄ alcohol ethacrylate esters, and mixturesthereof, with the C₁₋₄ alcohol acrylate esters, C₁₋₄ alcoholmethacrylate esters, and mixtures thereof, being most preferred. Thelong chain alcohol acrylate ester monomer is selected from C₈₋₄₀ alkylacrylate esters, with C₁₀₋₃₀ alkyl acrylate esters being preferred.

The crosslinking agent in both of these types of polymers is apolyalkenyl polyether of a polyhydric alcohol containing more than onealkenyl ether group per molecule, wherein the parent polyhydric alcoholcontains at least 3 carbon atoms and at least 3 hydroxyl groups.Preferred crosslinkers are those selected from the group consisting ofallyl ethers of sucrose and allyl ethers of pentaerythritol, andmixtures thereof. These polymers useful in the present invention aremore fully described in U.S. Pat. No. 5,087,445, to Haffey et al.,issued Feb. 11, 1992; U.S. Pat. No. 4,509,949, to Huang et al., issuedApr. 5, 1985; U.S. Pat. No. 2,798,053, to Brown, issued Jul. 2, 1957;which are incorporated by reference herein. See also, CTFA InternationalCosmetic Ingredient Dictionary, fourth edition, 1991, pp. 12 and 80;which are also incorporated herein by reference.

Examples of commercially availble hompolymers of the first type usefulherein include the carbomers, which are homopolymers of acrylic acidcrosslinked with allyl ethers of sucrose or pentaerytritol. Thecarbomers are available as the Carbopol® 900 series from B. F. Goodrich.Examples of commercially available copolymers of the second type usefulherein include copolymers of C₁₀₋₃₀ alkyl acrylates with one or moremonomers of acrylic acid, methacrylic acid, or one of their short chain(i.e. C₁₋₄ alcohol) esters, wherein the crosslinking agent is an allylether of sucrose or pentaerytritol. These copolymers are known asacrylates/C10-30 alkyl acrylate crosspolymers and are commericallyavailable as Carbopole® 1342, Pemulen TR-1, and Pemulen TR-2, from B. F.Goodrich. In other words, examples of carboxylic acid polymer thickenersuseful herein are those selected from the group consisting of carbomers,acrylates/C10-C30 alkyl acrylate crosspolymers, and mixtures thereof.

The compositions of the present can comprise from about 0.025% to about1%, more preferably from about 0.05% to about 0.75% and most preferablyfrom about 0.10% to about 0.50% of the carboxylic acid polymerthickeners.

Emulsifiers

The compositions herein can contain various emulsifiers. Theseemulsifiers are useful for emulsifying the various carrier components ofthe compositions herein, and are not required for solubilizing ordispersing the copolymers of the present invention. Suitable emulsifierscan include any of a wide variety of nonionic, cationic, anionic, andzwitterionic emulsifiers disclosed in the prior patents and otherreferences. See McCutcheon's, Detergents and Emulsifiers, North AmericanEdition (1986), published by Allured Publishing Corporation; U.S. Pat.No. 5,011,681 to Ciotti et al., issued Apr. 30, 1991; U.S. Pat. No.4,421,769 to Dixon et al., issued Dec. 20, 1983; and U.S. Pat. No.3,755,560 to Dickert et al., issued Aug. 28, 1973; these four referencesare incorporated herein by reference in their entirety.

Suitable emulsifier types include esters of glycerin, esters ofpropylene glycol, fatty acid esters of polyethylene glycol, fatty acidesters of polypropylene glycol, esters of sorbitol, esters of sorbitananhydrides, carboxylic acid copolymers, esters and ethers of glucose,ethoxylated ethers, ethoxylated alcohols, alkyl phosphates,polyoxyethylene fatty ether phosphates, fatty acid amides, acyllactylates, soaps and mixtures thereof.

Suitable emulsifiers can include, but are not limited to, polyethyleneglycol 20 sorbitan monolaurate (Polysorbate 20), polyethylene glycol 5soya sterol, Steareth-20, Ceteareth-20, PPG-2 methyl glucose etherdistearate, Ceteth-10, Polysorbate 80, cetyl phosphate, potassium cetylphosphate, diethanolamine cetyl phosphate, Polysorbate 60, glycerylstearate, PEG-100 stearate, and mixtures thereof. The emulsifiers can beused individually or as a mixture of two or more and can comprise fromabout 0.1% to about 10%, more preferably from about 1% to about 7%, andmost preferably from about 1% to about 5% of the compositions of thepresent invention.

Emollients

The compositions useful in the methods of the present invention can alsooptionally comprise at least one emollient. Examples of suitableemollients include, but are not limited to, volatile and non-volatilesilicone oils, highly branched hydrocarbons, and non-polar carboxylicacid and alcohol esters, and mixtures thereof. Emollients useful in theinstant invention are further described in U.S. Pat. No. 4,919,934, toDeckner et al., issued Apr. 24 1990, which is incorporated herein byreference in its entirety.

The emollients can typically comprise in total from about 1% to about50%, preferably from about 1% to about 25%, and more preferably fromabout 1% to about 10% by weight of the compositions useful in thepresent invention.

Additional Components

A variety of additional components can be incorporated into thecompositions herein. Non-limiting examples of these additionalcomponents include vitamins and derivatives thereof (e.g., ascorbicacid, vitamin E, tocopheryl acetate, retinoic acid, retinol, retinoids,and the like); low pH thickening agents (e.g. polyacrylamide and C₁₃₋₁₄isoparaffin and laureth-7, available as Sepigel from Seppic Corporation;polyquaternium and mineral oil, available as Salcare SC92, from AlliedColloids; crosslinked methyl quaternized dimethylaminomethacrylate andmineral oil, available as Salcare SC95 from Allied Colloids; resins;gums and thickeners such as xanthan gum, carboxymethyl cellulose,hydroxymethyl cellulose, hydroxyethyl cellulose, alkyl-modifiedhydroxyalkyl celluloses (e.g. long chain alkyl modified hydroxyethylcelluloses such as cetyl hydroxyethylcellulose), and magnesium aluminumsilicate; cationic polymers and thickeners (e.g., cationic guar gumderivatives such as guar hydroxypropyltrimonium chloride andhydroxypropyl guar hydroxypropyltrimonium chloride, available as theJaguar C series from Rhone-Poulenc; polymers for aiding the film-formingproperties and substantivity of the composition (such as a copolymer ofeicosene and vinyl pyrrolidone, an example of which is available fromGAF Chemical Corporation as Ganex® V-220); suspending agents such asethylene glycol distearate and the like; preservatives for maintainingthe antimicrobial integrity of the compositions; skin penetration aidssuch as DMSO, 1-dodecylazacycloheptan-2-one (available as Azone from theUpjohn Co.) and the like; antioxidants; chelators and sequestrants; andaesthetic components such as fragrances, colorings, essential oils, skinsensates, astringents, skin soothing agents, skin healing agents and thelike, nonlimiting examples of these aesthetic components includepanthenol and derivatives (e.g. ethyl panthenol), pantothenic acid andits derivatives, clove oil, menthol, camphor, eucalyptus oil, eugenol,menthyl lactate, witch hazel distillate, allantoin, bisabalol,dipotassium glycyrrhizinate and the like.

Method of Using Hair and Skin Care Compositions

The hair care and skin care compositions of the present invention areused in conventional ways to provide the desired benefit appropriate tothe product such as hair styling, holding, cleansing, conditioning andthe like for hair care compositions and benefits such as moisturization,sun protection, anti-acne, anti-wrinkling, artificial tanning,analgesic, and other cosmetic and pharmaceutical benefits for skin carecompositions. Such methods of use depend upon the type of compositionemployed but generally involve application of an effective amount of theproduct to the hair or skin, which may then be rinsed from the hair orskin (as in the case of shampoos and some conditioning products) orallowed to remain on the hair (as in the case of spray, mousse, or gelproducts), or allowed to remain on the skin (as in the case of the skincare compositions). By "effective amount" is meant an amount sufficientto provide the benefit desired. Preferably, hair rinse, mousse, and gelproducts are applied to wet or damp hair prior to drying and styling ofthe hair. After such compositions are applied to the hair, the hair isdried and styled in the usual ways of the user. Hair sprays aretypically applied to dry hair after it has already been dried andstyled. Cosmetic and pharmaceutical topical skin care compositions areapplied to and rubbed into the skin.

The following examples further illustrate preferred embodiments withinthe scope of the present invention. The examples are given solely forthe purposes of illustration and are not to be construed as limitationsof the present invention as many variations of the invention arepossible without departing from its spirit and scope.

EXAMPLES

The following examples further describe and demonstrate embodimentswithin the scope of the present invention. The examples are given solelyfor the purpose of illustration and are not to be construed aslimitations of the present invention, as many variations thereof arepossible without departing from the spirit and scope of the invention.

Ingredients are identified by chemical or CTFA name.

Example I

Synthesis of Poly(2-ethyl-2-oxazoline) Alcohol

To a solution of 50 g (0.5044 mol) of 2-ethyl-2-oxazoline in 50 mL ofacetonitrile is added 0.92 g (0.0048 mol) of methyl-p-toluenesulfonateat 0° C. under a nitrogen atmosphere. The reaction mixture is heated at80° C. for 20 hours and the resulting polymer solution is then refluxedwith 2.3 mL distilled water in the presence of 5.6 g (0.0528 mol) ofsodium carbonate for 24 hours. The solvents are removed under vacuum.The residue is extracted with 300 mL of dichloromethane for 24 hours,and the insolubles are removed by suction filtration. Thedichloromethane is then evaporated to yield about 48 g (96% yield) ofpoly(2ethyl-2-oxazoline) alcohol.

Example II

Synthesis of Acrylate-Capped Poly(2-ethyl-2-oxazoline) AlcoholMacromonomer

To a solution of 48 g of poly(2-ethyl-2-oxazoline) alcohol (from EXAMPLEI) and 1.0 g (0.01056 mol) of triethylamine in 80 mL of dichloromethaneis added dropwise a solution of 0.95 g (0.01056 mol) of acryloylchloride at 0° C. under a nitrogen atmosphere. The reaction mixture isthen stirred at room temperature for 36 hrs, and the resulting solutionis then suction filtered to remove the insolubles. The solvent and anyunreacted triethylamine are removed by evaporation under vacuum. Theresulting solid is then redissolved in 200 mL of dichloromethane,filtered, and evaporated under vacuum to yield about 45.6 g (95% yield)of the macromonomer.

Using an analogous procedure the methacrylate and ethacrylate endcappedmacromonomers are prepared by replacing the acryloyl chloride with anequivalent molar amount of methacryloyl chloride and ethacryloylchloride, respectively.

Example III

Synthesis of Vinvibenzyl-Capped Poly(2-ethyl-2-oxazoline) AlcoholMacromonomer

To a solution of 50 g (0.5044 mol) of 2-ethyl-2-oxazoline in 50 mL ofacetonitrile is added a mixture of 0.3816 g (0.0025 mol) of meta andparavinylbenzylchlorides (available from Aldrich Chemical Co.), 0.562 g(0.0037 mol) of sodium iodide and 0.06 g (0.00023 mol) ofN,N'-diphenyl-p-phenylenediamine. The solution is then heated at 90° C.for 16 hours. To the resulting reaction product is added 100 mL ofdichloromethane and the solution is filtered and then precipitated in800 mL of ether. The precipitate product is collected by vacuumfiltration and dried under vacuum at ambient temperature to yield about45 g (90% yield) of the macromonomer.

Example IV

Synthesis of Acrylate-Capped Poly(ethylene glycol)methyl EtherMacromonomer

To a solution of 50 g (0.01 mol) of poly(ethylene glycol)methyl etherhaving an average molecular weight of about 5000 (commercially availablefrom Aldrich Chemical Co.) and 4.05 g (0.04 mol) of triethylamine in 400mL of dichloromethane is added dropwise at 0° C. under a nitrogenatmosphere a solution of 2.26 g (0.025 mol) of acryloyl chloridedissolved in 25 mL of dichloromethane. The reaction mixture is thenstirred at room temperature for 36 hrs, and the resulting solution isthen suction filtered to remove the insolubles. The solvent and anyunreacted triethylamine are removed by evaporation under vacuum. Theresulting solid is then redissolved in 300 mL of dichloromethane,filtered, and evaporated under vacuum to yield about 50 g (100% yield)of the macromonomer.

The above procedure is varied using other poly(ethylene glycol)alkylethers (e.g. methyl, ethyl, 2-ethylhexyl, decyl, dodecyl, cetyl,stearyl, lauryl, and myristyl wherein the polymer has an averagemolecular weight varying from about 1000 to about 200,000) to obtain theanalogous acrylate-capped macromonomers. Additionally, the methacrylateand ethacrylate endcapped macromonomers are prepared by replacing theacryloyl chloride with an equivalent molar amount of methacryloylchloride and ethacryloyl chloride, respectively.

Example V

Synthesis of Poly(n-butyl acrylate)-graft-poly(2-ethyl-2-oxazoline)Thermoplastic Elastomeric Copolymer

To a solution of 16.0 g (0.1248 mol) of n-butyl acrylate, and 4 g ofacrylate capped poly(2-ethyl-2-oxazoline) macromonomer (from Example II)in 100 mL of acetone is added 0.03 g (0.00018 mol) ofazoisobutyronitrile (AIBN) initiator. The resulting solution is refluxedslowly for about 20 hours. The reaction is then quenched by the additionof about 5 mL of methanol. The solution is then poured into a teflon panand the acetone is evaporated at room temperature under a fume hood. Theresulting polymer film is redissovied in ethanol, filtered, and theethanol is then evaporated to yield about 18.4 g of the thermoplasticelastomeric copolymer.

Alternatively, by varying the monomers and macromoners used, thisprocedure is used to prepare other copolymers of the present invention.

EXAMPLE VI

Synthesis ofPoly(n-butyl-co-2-methoxvethylacrylate)-graft-poly(2-ethyl-2-oxazoline)Thermoplastic Elastomeric Copolymer: Method I

To a solution of 4.5 g (0.035 mol) of n-butyl acrylate, 2.5 g (0.0192mol) of 2-methoxy ethylacrylate and 3 g poly(2-ethyl-2-oxazoline)macromonomer (from Example II) in 40 mL of acetone is added 0.05 g ofAIBN initator. The resulting solution is refluxed slowly for about 20hours. The reaction is then quenched by the addition of about 5 mL ofmethanol. The solution is then poured into a teflon pan and the acetoneis evaporated at room temperature under a fume hood. The resultingpolymer film is redissovled in ethanol, filtered, and the ethanol isthen evaporated to yield about 9.5 g of the thermoplastic elastomericcopolymer.

Alternatively, by varying the monomers and macromoners used, thisprocedure is used to prepare other copolymers of the present invention.

Example VII

Synthesis ofPoly(n-butyl-co-2-methoxyethvlacrylate)-graft-poly(2-ethyl-2-oxazoline)Thermoplastic Elastomeric Corolymer: Method II

To a 500 mL round-bottomed flask is added 20.8 g (0.1623 mol) of n-butylacrylate, 11.2 g (0.0861 mol) of 2-methoxyethyl acrylate, 0.30 g (0.002mol) 2-vinylbenzyl chloride, and 0.02 g (0.0012 mol) ofazoisobutyronitrile (AIBN) initator, in 200 mL of acetone. The resultingsolution is refluxed slowly for about 24 hours. The reaction is thenquenched by the addition of about 5 mL of methanol and cooled to roomtemperature. The solvents are removed by rotary evaporation and theresulting polymer is dissolved in 250 mL of dry acetonitrile. Next 20.0g (0.2018 mol) of 2-ethyl-2-oxazoline and 0.44 g (0.0029 mol) of sodiumiodide is added and the solution is heated to 90° C. for 20 hours. Theresulting solution is filtered and the solvent is evaporated to yieldabout 45.0 g (86% yield) of the thermoplastic elastomeric copolymer.

Alternatively, by varying the monomers used, this procedure is used toprepare other copolymers of the present invention.

Example VIII

Synthesis of Poly(n-butyl-co-2-(dimethylamino)ethylmethacrylate)-graft-poly(2-ethyl-2-oxazoline) Thermoplastic Elastomeric

To a solution of 7.2 g (0.0561 mol) of n-butyl acrylate, 4.8 g (0.0305mol) of 2-(dimethylamino)ethyl methacrylate, and 8.0 gpoly(2-ethyl-2-oxazoline) macromonomer (from Example II) in 80 mL ofacetone is added 0.01 g of AIBN initator. The resulting solution isrefluxed slowly for about 24 hours. The reaction is then quenched by theaddition of about 5 mL of methanol. The solution is then poured into ateflon pan and the acetone is evaporated at room temperature under afume hood. The resulting polymer film is redissovled in ethanol,filtered, and the ethanol is then is evaporated to yield about 18.4 g ofthe thermoplastic elastomeric copolymer.

Alternatively, by varying the monomers and macromoners used, thisprocedure is used to prepare other copolymers of the present invention.

Example IX

Synthesis of Methyl Quaternized Poly(n-butyl-co-2-(dimethylamino)-ethylmethacrylate)graft-poly(2-ethyl-2-oxazoline) Thermoplastic ElastomericCopolymer

To 10 grams of the copolymer from EXAMPLE VIII dissovled in 80 grams ofethanol is added dropwise 4.32 g (0.0281 mole) of dimethylsulfate. Theresulting solution is stirred for 2 hours at room temperature. Thesolvent is removed by rotary evorpation to yield about 10 grams of themethyl quaternized copolymer.

Example X

Hair Spray

Hair spray compositions are prepared from the following componentsutilizing conventional mixing techniques.

    ______________________________________                                                     Weight %                                                         Ingredients    A       B        C     D                                       ______________________________________                                        Water          QS 100  QS 100   QS 100                                                                              QS 100                                    Ethanol (SCA 40) 79.0   79.0  79.0  90.0                                      Copolymer of Example VI.sup.1 4.0 4.0 3.0 3.0                                 Fragrance 0.1 0.2 -- --                                                     ______________________________________                                         .sup.1 Alternatively, spray compositions are prepared using the copolymer     of Examples V, VIII, XXII, XXIII, XXIV, and XXVI.                        

These products are prepared by first dissolving the polymer in theethanol with stirring. The water and fragrance are then added withstirring. The resulting hair spray compositions can then be packaged ina nonaerosol spray pump. Alternatively, the compositions can be combinedwith conventional propellants and packaged in an aerosol spray.

These hair sprays are useful for application to the hair to provide astyling and holding benefit.

Example XI

Reduced Volatile Organic Content Hairspray

Hair spray compositions are prepared from the following componentsutilizing conventional mixing techniques.

    ______________________________________                                        Ingredients    A       B        C     D                                       ______________________________________                                        Water          QS 100  QS 100   QS 100                                                                              QS 100                                    Ethanol 54.0   54.0  54.0  54.0                                               Copolymer of Example VI.sup.1 4.0 3.0 4.0 3.0                                 Fragrance  0.05 0.2 -- --                                                   ______________________________________                                         .sup.1 Alternatively, spray compositions are prepared using the copolymer     of Examples V, VIII, XXII, XXIII, XXIV, and XXVI.                        

These products are prepared by first dissolving the polymer in theethanol with stirring. The water and fragrance are then added withstirring. The resulting hair spray compositions can then be packaged ina nonaerosol spray pump. Alternatively, the compositions can be combinedwith conventional propellants and packaged in an aerosol spray.

These hair sprays are useful for application to the hair to provide astyling and holding benefit.

Example XII

Mousse

Mousse compositions are prepared from the following components utilizingconventional mixing techniques.

    ______________________________________                                                       Weight %                                                       Ingredients        A       B         C                                        ______________________________________                                        Water              QS 100  QS 100    QS 100                                     Copolymer of Example VIII.sup.1 3.00 2.50 3.50                                Lauramide DEA 0.33 0.33 0.33                                                  Sodium Methyl Oleyl Taurate 1.67 1.67 1.67                                    DMDM Hydantoin 0.78 0.78 0.78                                                 Disodium EDTA 0.20 0.20 0.20                                                  Polyoxyalkylated isostearyl alcohol.sup.2 0.10 0.10 0.10                      Fragrance 0.10 0.10 0.10                                                      Propellant.sup.3 7.0  7.0  7.0                                              ______________________________________                                         .sup.1 Alternatively, mousse compositions are prepared using the              copolymers of Examples V, VI, XXII, XXIII, XXIV, and XXVI.                    .sup.2 Available as Aerosurf 66E10.                                           .sup.3 Available as a mixture of 82.46% isobutane, 16.57% propane, and        0.001% butane.                                                           

These products are prepared by first dissolving the polymer in waterwith stirring. The remaining ingredients, except the propellant, arethen added with stirring.

The resulting mousse concentrate can then be combined with conventionalpropellants (e.g., Propellant A46) and packaged in an aerosol spray.

These mousses are useful for application to the hair to provide astyling and holding benefit.

Example XIII

Hair Tonic

Hair tonic compositions are prepared from the following componentsutilizing conventional mixing techniques.

    ______________________________________                                                      Weight %                                                        Ingredients     A         B       C                                           ______________________________________                                        Ethanol         QS 100    QS 100  QS 100                                        Copolymer of Example VI.sup.1 0.75 1.00 1.25                                  Fragrance 0.10 0.20 0.30                                                    ______________________________________                                         .sup.1 Alternatively, tonic compositions are prepared using the copolymer     of Examples, V, VIII, XXII, XXIII, XXIV, and XXVI.                       

These products are prepared by dissolving the polymer in the ethanolwith stirring and then adding the fragrance and any colors.

These hair tonics are useful for application to the hair to provide astyling and holding benefit.

Example XIV

Hair Conditioner

A hair conditioner composition is prepared from the following componentsutilizing conventional mixing techniques.

    ______________________________________                                        Ingredient           Weight %                                                 ______________________________________                                        Styling Agent Premix                                                            Copolymer of Example IX 1.00                                                  Silicone Premix                                                               Silicone gum, GE SE76.sup.1 0.30                                              Octamethyl cyclotetrasiloxane 1.70                                            Main Mix                                                                      Water QS 100                                                                  Cetyl Alcohol 1.00                                                            Quaternium 18.sup.2 0.85                                                      Stearyl Alcohol 0.70                                                          Hydroxethyl cellulose 0.50                                                    Ceteareth-20 0.35                                                             Fragrance 0.20                                                                Dimethicone copolyol 0.20                                                     Citric Acid 0.13                                                              Methylchloroisothiazolinone (and)                                             methylisothiazolinone 0.04                                                    Sodium Chloride 0.01                                                        ______________________________________                                         .sup.1 Commercially available from General Electric.                          .sup.2 Dimethyl Di(Hydrogenated Tallow) Ammonium Chloride                

The product is prepared by comixing all the Main Mix ingredients,heating to about 60° C. with mixing, and colloid milling while coolingto about 45° C. At this temperature, the two premixies are addseparately with moderate agitation and the resultatn conditioner isallowed to cool to room temperature.

This product is useful as a rinse off hair conditioner.

Example XV

Shampoo Composition

A shampoo composition is prepared from the following componentsutilizing conventional mixing techniques.

    ______________________________________                                        Ingredients          Weight %                                                 ______________________________________                                        Styling Agent                                                                   Copolymer from Example IX 1.00                                                Premix                                                                        Silicone gum 0.50                                                             Dimethicone, 350 cs fluid 0.50                                                Main Mix                                                                      Water QS 100                                                                  Ammonium lauryl sulfate 11.00                                                 Cocamide MEA 2.00                                                             Ethylene glycol distearate 1.00                                               Xanthan Gum 1.20                                                              Methylchloroisothiazolinone (and) 0.04                                        methylisothiazolinone                                                         Citric Acid to pH 4.5 as needed                                             ______________________________________                                    

The Main Mix is prepared by first dissolving the xanthan gum in thewater with conventional mixing. The remaining Main Mix ingredients areadded and the Main Mix is heated to 150° F. with agitation for 1/2 hour.The Styling Agent and the Premix are then added sequentially with about10 minutes of agitation between additions, and the entire mixture isstirred while the batch is cooled to room temperature. For variedparticile size, the Styling AGent and Premix can be added at differenttimes using either or both high shear mixing (high speed dispersator) ornormal agitation.

This shampoos is useful for cleansing the hear and for providing astyling benefit.

Example XVI

Anti-Acne Composition

An anti-acne composition is made by combining the following componentsusing conventional mixing technology.

    ______________________________________                                        Ingredient         Weight %                                                   ______________________________________                                        Water              QS 100                                                       Salicylic Acid 2.0                                                            Copolymer from Example VI.sup.1 2.0                                           Ethanol (SDA 40) 40.0                                                       ______________________________________                                         .sup.1 Alternatively, the antiacne compositions are prepared using the        copolymers of Examples VIII, IX, XXII, XXIII, XXIV, and XXVI.            

The compositon display skin penetration of the salicylic acid as well asimproved skin reel and residue characteristics and is useful for thetreatment of acne.

Example XVII

Topical Analgesic Composition

A topical analgesic composition is made by combining the followingingredients utilizing conventional mixing techniques.

    ______________________________________                                        Ingredient         Weight %                                                   ______________________________________                                        Water, Purified    QS 100                                                       Ibuprofen 2.0                                                                 Copolymer from Example VI.sup.1 2.0                                           Ethanol (SDA 40) 20.0                                                       ______________________________________                                         .sup.1 Alternatively, the topical analagesic compositions are prepared        using the copolymers of Examples VIII, IX, XXII, XXIII, XXIV, and XXVI.  

The compositions display skin penetration of the ibuprofen active aswell as improved skin feel and residue characteristics together withexcellent moisturizing, emolliency, rub-in and absorptioncharacteristics.

Example XVIII

Sunless Tanning Composition

A composition for sunless tanning is made by combining the followingingredients utilizing conventional mixing techniques.

    ______________________________________                                        Ingredients            Weight %                                               ______________________________________                                        Phase A                                                                         Water qs 100                                                                  Copolymer from Example VI                                                                          .sup.1 2.00                                              Carbomer 934.sup.2 0.20                                                       Carbomer 980.sup.3 0.15                                                       Acrylic Acid Copolymer.sup.4 0.15                                             Phase B                                                                       PPG-20 Methyl Glucose Ether Distearate 2.00                                   Tocopheryl Acetate 1.20                                                       Mineral Oil 2.00                                                              Stearyl Alcohol 1.00                                                          Shea Butter 1.00                                                              Cetyl Alcohol 1.00                                                            Ceteareth-20 2.50                                                             Ceteth-2 1.00                                                                 Ceteth-10 1.00                                                                Phase C                                                                       DEA-Cetyl Phosphate 0.75                                                      Phase D                                                                       Dihydroxyacetone 3.00                                                         Phase E                                                                       Butylene Glycol 2.00                                                          DMDM Hydantoin (and)                                                          Iodopropynyl Butylcarbamate 0.25                                              Phase F                                                                       Fragrance 1.00                                                                Cyclomethicone 2.00                                                         ______________________________________                                         .sup.1 Alternatively, the artificial tanning compositions are prepared        using the copolymers of Examples VIII and IX.                                 .sup.2 Available as Carbopol ® 934 from B. F. Goodrich.                   .sup.3 Available as Carbopol ® 980 from B. F. Goodrich.                   .sup.4 Available as Pemulen TR1 from B. F. Goodrich.                     

In a suitable vessel the Phase A ingredients are dispersed in the waterand heated to 75-85° C. In a separate vessel the Phase B ingredients arecombined and heated to 85-90° C. until melted. Next, the DEA-CetylPhosphate is added to the liquid Phase B and stirred until dissolved.This mixture is then added to Phase A to form the emulsion. The emulsionis cooled to 40-45° C. with continued mixing. Next, in a separatevessel, the dihydroxyacetone is dissolved in water and the resultingsolution is mixed into the emulsion. In another vessel, the Phase Eingredients are heated with mixing to 40-45° C. until a clear solutionis formed and this solution is then added to the emulsion. Finally, thePhase F ingredients are added to the emulsion with mixing, which is thencooled to 30-35° C., and then to room temperature.

This emulsion is useful for topical application to the skin to providean artificial tan.

Example XIX

Sunscreen Composition

An oil-in-water emulsion is prepared by combining the followingcomponents utilizing conventional mixing techniques.

    ______________________________________                                        Ingredients         Weight %                                                  ______________________________________                                        Phase A                                                                         Water QS 100                                                                  Carbomer 954.sup.1 0.24                                                       Carbomer 1342.sup.2 0.16                                                      Copolymer from Example VI.sup.3 1.75                                          Disodium EDTA 0.05                                                            Phase B                                                                       Isoarachidyl Neopentanoate.sup.4 2.00                                         PVP Eicosene Copolymer.sup.5 2.00                                             Octyl Methoxycinnamate 7.50                                                   Octocrylene 4.00                                                              Oxybenzone 1.00                                                               Titanium Dioxide 2.00                                                         Cetyl Palmitate 0.75                                                          Stearoxytrimethylsilane 0.50                                                  (and) Stearyl Alcohol.sup.6                                                   Glyceryl Tribehenate.sup.7 0.75                                               Dimethicone 1.00                                                              Tocopheryl Acetate 0.10                                                       DEA-Cetyl Phosphate 0.20                                                      Phase C                                                                       Water 2.00                                                                    Triethanolamine 99% 0.60                                                      Phase D                                                                       Water 2.00                                                                    Butylene Glycol 2.00                                                          DMDM Hydantoin (and) 0.25                                                     Iodopropynyl Butylcarbamate.sup.8                                             dL Panthenol 1.00                                                             Phase E                                                                       Cyclomethicone 1.00                                                         ______________________________________                                         .sup.1 Available as Carbopol ® 954 from B. F. Goodrich.                   .sup.2 Available as Carbopol ® 1342 from B. F. Goodrich.                  .sup.3 Alternatively, the sunscreen compositions are prepared using the       copolymers of Examples VIII and IX.                                           .sup.4 Available as Elefac I205 from Bernel Chemical.                         .sup.5 Available as Ganex V220 from GAF Corporation.                          .sup.6 Available as DC 580 Wax from Dow Corning.                              .sup.7 Available as Synchrowax HRC from Croda.                                .sup.8 Available as Glydant Plus from Lonza.                             

In a suitable vessel the Phase A ingredients are dispersed in the waterand heated to 75-85° C. In a separate vessel the Phase B ingredients(except DEA-Cetyl Phosphate) are combined and heated to 85-90° C. untilmelted. Next, the DEA-Cetyl Phosphate is added to the liquid Phase B andstirred until dissolved. This mixture is then added to Phase A to formthe emulsion. The Phase C ingredients are combined until dissolved andthen added to the emulsion. The emulsion is then cooled to 40-45° C.with continued mixing. In another vessel, the Phase D ingredients areheated with mixing to 40-45° C. until a clear solution is formed andthis solution is then added to the emulsion. Finally, the emulsion iscooled to 35° C. and the Phase E ingredient is added and mixed.

This emulsion is useful for topical application to the skin to provideprotection from the harmful effects of ultraviolet radiation.

Example XX

Facial Moisturizer

A leave-on facial emulsion composition containing a cationic hydrophobicsurfactant is prepared by combining the following components utilizingconventional mixing techniques.

    ______________________________________                                        Ingredient           Weight %                                                 ______________________________________                                        Water                QS 100                                                     Copolymer from Example VI.sup.1 1.00                                          Glycerin 3.00                                                                 Cetyl Palmitate 3.00                                                          Cetyl Alcohol 1.26                                                            Quaternium-22 1.00                                                            Glyceryl Monohydroxy Stearate 0.74                                            Dimethicone 0.60                                                              Stearic Acid 0.55                                                             Octyldodecyl Myristate 0.20                                                   Carbomer 1342  0.125                                                          Tetrasodium EDTA 0.10                                                         DMDM Hydantoin and Iodopropynyl 0.10                                          Butyl Carbamate                                                               Carbomer 951  0.075                                                         ______________________________________                                         .sup.1 Alternatively, the moisturizers are prepared using the copolymers      of Examples VIII, IX, XXII, XXIII, XXIV, and XXVI.                       

This emulsion is useful for application to the skin as a moisturizer.

Example XXI

Styryl Capped Poly(2-vinyl pyridine) Macromonomer

Approximately 800 mL of dry tetrahydrofuran is placed in a round bottomflask equipped with a mechanical stirrer and a thermometer and is cooledto -78° C. using a dry ice/isopropanol bath. Next 7.69 grams (0.01 mole)of sec-butyl lithium (1.3 Molar solution in hexane) and 1.89 grams(0.0124 mole) of diphenylethylene are added. The mixture is then allowedto stir for 5 minutes. Next, 2-vinyl pyridine (105 grams, 1.0 moles) isadded dropwise with stirring. After the addition is complete, 2.29 grams(0.15 mole) of para-vinyl benzyl chloride is added, and the reactionmixture is allowed to warm to room temperature with stirring. Thereaction product is then carefully poured into I liter of n-hexamessolvent to precipitate the macromonomer. The macromonomer is isolated bysuction filtration followed by drying under vacuum to yield 97.0 grams(92% yield) of styryl capped poly(2-vinyl pyridine) macromonomer.

Using the above procedure, the following monomers are used to preparetheir corresponding macromonomers: 3-vinylpyridine, 4-vinylpyridine,4-vinyl aminomethylbenzene, 4-vinyl dimethylaminomethylbenzene,2-vinyl-5-chloropyridine, 2-vinyl4-methylpyridine, and 4-vinyldimethylaminoethylbenznen.

Example XXII

Synthesis Of Poly(n-ButylAcrylate-Co-2-Methoxyethylacrylate)-Graft-Poly(2-Vinylpyridine)

To a solution of 16.0 g (0.1248 mol) of n-butyl acrylate, and 4 g ofstyryl capped poly(2-vinyl pyridine) macromonomer (from Example XI) in100 mL of acetone is added 0.03 g (0.00018 mol) of azoisobutyronitrile(AIBN) initiator. The resulting solution is refluxed slowly for about 20hours. The reaction is then quenched by the addition of about 5 mL ofmethanol. The solution is then poured into a teflon pan and the acetoneis evaporated at room temperature under a fume hood. The resultingpolymer film is redissovled in ethanol, filtered, and the ethanol isthen evaporated to yield about 18.4 g of the thermoplastic elastomericcopolymer.

Alternatively, by varying the monomers and macromoners used, thisprocedure is used to prepare other copolymers of the present invention.

Example XXIII

Synthesis Of Methyl Quaternized Polymer Of Example XII

To 5 grams of the copolymer from example XXII dissolved in 80 grams ofethanol is added dropwise 2.16 grams (0.0140 mole) of dimethylsulfate.The resulting solution is stirred for 2 hours at room temperature. Thesolvent is removed by rotary evaporation to yield the methyl quaternizedcopolymer.

Example XXIV

Synthesis Of Hydrochloride Salt Of Polymer Of Example XXII

To 5 grams of the copolymer from Example XXII dissolved in 80 grams ofethanol is bubbled in hydrogen chloride gas for approximately 15minutes. The solvent is removed by rotary evaporation to yield thehydrochloride salt of the copolymer.

Example XXV

Styryl Capped Poly(N,N-Dimethylacrylamide)

Using the procedure of Example XXI, 99 grams, (1.0 mole) ofN,N-dimethylacrylamide is used instead of 2-vinylpyridine.

In an alternative procedure, the corresponding styryl cappedpoly(N,N-dimethylmethylacrylamide) is prepared usingN,N-dimethylmethacrylamide.

Example XXVI

Synthesis Of Poly(n-ButylAcrylate-Co-2-Methoxyethylacrylate)-Graft-[Poly(2-N,N-Dimethylacrylamide)

Using the method of Example XXII, 4.0 grams of styryl cappedpoly(N,N-dimethylacrylamide) is used to replace the styryl cappedpoly(2-vinylpyridine).

What is claimed is:
 1. A water or alcohol soluble or dispersiblethermoplastic elastomeric copolymer having a backbone and two or morepolymeric side chains, said copolymer formed from the copolymerizationof randomly repeating A and B units wherein said copolymer comprises:(i)from about 40% to about 90% by weight of said A units, wherein said Aunits are polymerizable monomer units; and (ii) from about 10% to about60% by weight of said B units, wherein said B units are hydrophilicmacromonomer units, copolymerizable with A, whereby said macromonomerunits form said polymeric side chains; and wherein said B macromonomerunits are selected from nitrogen containing macromonomers represented bythe following structure ##STR13## wherein R¹² is selected from the groupconsisting of hydrogen, C₁ -C₆ straight or branched chain alkyl, benzyl,and mixtures thereof m is an integer from about 10 to about 2000; E isan ethyleneically unsaturated moiety, copolymerizable with A, selectedfrom the group consisting of vinyl, allyl, acryloyl, methacryloyl,ethacryloyl, styryl, 2-vinyl benzyl, 3-vinyl benzyl, 4-vinyl benzyl,2-vinylbenzoyl, 3-vinylbenzoyl, 4-vinylbenzoyl, 1-butenyl, isobutenyl,isoprenyl, cyclopentenyl, cyclohexenyl, and mixtures thereof; and P isselected from the group consisting of pharmaceutically acceptable saltsor C₁ -C₃₀ straight or branched chain alkyl quaternized derivatives of2-pyridyl, 3-pyridyl, 4-pyridyl, 4-dimethylaminomethyl benzene,4-aminomethyl benzene, 4-dimethylaminoethyl benzene, 4-aminoethylbenzene, and mixtures thereof;wherein said copolymer has a weightaverage molecular weight greater than about 10,000, and wherein saidcopolymer exhibits two distinct T_(g) values, said first T_(g)corresponding to said backbone and having a value less than about 0° C.,and said second T_(g) corresponding to said polymeric side chains andhaving a value greater than about 25° C.
 2. A copolymer according toclaim 1 wherein R¹² is 1,1-diphenyl-4-methylpentyl and m is an integerfrom about 20 to about
 250. 3. A copolymer according to claim 2 whereinP is selected from the group consisting of hydrochloride andhydrobromide salts of 2-pyridyl, 3-pyridyl, 4-pyridyl, methyl and ethylquaternized derivatives of 2-pyridyl, 3-pyridyl, 4-pyridyl, and mixturesthereof.
 4. A copolymer according to claim 2 wherein P is methylquaternized 2-pyridyl.
 5. A copolymer according to claim 4 wherein theT_(g) corresponding to said backbone is from about -45° C. to about-120° C., and the T_(g) corresponding to said hydrophilic polymeric sidechains is from about 35° C. to about 150° C.
 6. A copolymer according toclaim 4 wherein said A monomer units comprise from about 50% to about85% by weight of the total copolymer and said B macromonomer unitscomprise from about 15% to about 50% by weight of the total copolymer.7. A copolymer according to claim 6 wherein said A monomer unitscomprise from about 60% to about 80% by weight of the total copolymerand said B macromonomer units comprise from about 20% to about 40% byweight of the total copolymer.
 8. A copolymer according to claim 7wherein said A monomer units are of the formula ##STR14## wherein X isselected from the group consisting of --OH, --OM, --OR⁴, --NH₂, --NHR⁴,and --N(R⁴)₂ ; M is a cation selected from the group consisting of Na+,K+, Mg++, Ca++, Zn++, NH₄ +, alkylammonium, dialkylammonium,trialkylammonium, and tetralkylammonium; R⁴ is selected from the groupconsisting of H, C₁ -C₈ straight or branched chain alkyl,N,N-dimethylaminoethyl, methyl quatemized N,N-dimethylaminoethyl,2-hydroxyethyl, 2-methoxyethyl, and 2-ethoxyethyl; and R⁵ and R⁶ areindependently selected from the group consisting of H, C₁ -C₈ straightor branched chain alkyl, methoxy, ethoxy, 2-hydroxyethyl,2-methoxyethyl, and 2ethoxyethyl.
 9. A copolymer according to claim 8wherein said A monomer units are selected from the group consisting ofn-butyl acrylate, 2-ethylhexyl acrylate, N-octyl acrylamide,2-methoxyethyl acrylate, 2-hydroxyethyl acrylate, N,N-dimethylaminoethylacrylate, methyl quaternized N,N-dimethylaminoethyl acrylate, andmixtures thereof.
 10. A water or alcohol soluble or dispersiblethermoplastic elastomeric copolymer having a backbone and one or morepolymeric side chains, said copolymer formed from the copolymerizationof randomly repeating A and B units and corresponding to the formula

    [A].sub.a [B].sub.b

wherein (i) A is at least one polymerizable monomer unit correspondingto the formula ##STR15## wherein X is selected from the group consistingof --OH, --OM, --OR⁴, --NH₂, --NHR⁴, and --N(R⁴)₂ ; M is a cationselected from the group consisting of Na+, K+, Mg++, Ca++, Zn++, NH₄ +,alkylammonium, dialkylammonium, triallylammonium, and tetralkylammonium;each R⁴ is selected from the group consisting of H, C₁ -C₈ straight orbranched chain allyl, N,N,-dimethylaminoethyl, 2-hydroxyethyl,2-methoxyethyl, and 2-ethoxyethyl; and R⁵ and R⁶ are independentlyselected from the group consisting of H, C₁ -C₈ straight or branchedchain alkyl, methoxy, ethoxy, 2-hydroxyethoxy, 2-methoxyethyl, and2-ethoxyethyl; (ii) B is at least one hydrophilic nitrogen containingmacromonomer unit copolymerizable with A corresponding to the formula##STR16## wherein R¹² is selected from the group consisting of hydrogen,C₁ -C₆ straight or branched chain allyl benzyl, and mixtures thereof mis an integer from about 10 to about 2000; E is an ethylenicallyunsaturated moiety, copolymerizble with A and C, selected from the groupconsisting of vinyl, allyl, acryloyl, methacryloyl, ethacryloyl, styryl,2-vinyl benzyl, 3-vinyl benzyl, 4-vinyl benzyl, 2-vinylbenzoyl,3-vinylbenzoyl, 4-vinylbenzoyl, 1-butenyl, isobutenyl, isoprenyl,cyclopentyl, cyclohexenyl, and mixtures thereof, and P is selected fromthe group consisting of pharmaceutically acceptable salts and C₁ -C₃₀straight or branched chain alkyl quaternized derivatives of 2-pyridyl,3-pyridyl, 4-pyridyl, 4-dimethylaminoethyl benzene, 4-aminoethylbenzene, 4-dimethylaminoethyl benzene, 4-aminoethyl benzene, andmixtures thereof; (iii) a is an integer of about 100 or greater and b isan integer of about 2 or greater; andwherein said copolymer exhibits twodistinct T_(g) values, said first T_(g) corresponding to said backboneand having a value less than about 0° C., and said second T_(g)corresponding to said polymeric side chains and having a value greaterthan about 25° C.
 11. A copolymer according to claim 10 wherein said Amonomer units are selected from the group consisting of n-butylacrylate, 2-ethylhexyl acrylate, N-octyl acrylamide, 2-methoxyethylacrylate, 2-hydroxyethyl acrylate, N,N-dimethylaminoethyl acrylate, andmixtures thereof; R is methyl, R' is ethyl, m is an integer from about10 to about 2000, a is an integer from about 100 to about 3000, and b isan integer from about 2 to about
 50. 12. A hair care composition usefulfor styling hair, comprising the copolymer of claim 1 and a carriersuitable for application to the hair.
 13. A hair care compositionaccording to claim 12, in the form of a liquid suitable for applicationto the hair, wherein said carrier comprises water, a C1-C6 monohydricalcohol, or a mixture thereof.
 14. A hair care composition according toclaim 13 which further comprises a propellant.
 15. A hair carecomposition according to claim 12, in the form of a liquid suitable forapplication to the hair, wherein said carrier comprises a solventselected from the group consisting of water, methanol, ethanol,isopropanol, and mixtures thereof.
 16. A hair care composition accordingto claim 12, in the form of a mousse for application to the hair,wherein said carrier comprises water, one or more surfactants, and apropellant.
 17. A composition for topical application to the skincomprising the copolymer of claim 1 and a carrier suitable forapplication to the skin.
 18. A water or alcohol soluble or dispersiblethermoplastic elastomeric copolymer having a backbone and two or morepolymeric side chains, said copolymer formed from the copolymerizationof randomly repeating A and B units wherein said copolymer comprises:(i)from about 50% to about 85% by weight of said A units, wherein said Aunits are polymerizable monomer units; and said A monomer units are ofthe formula ##STR17## wherein X is selected from the group consisting of--OH, --OM, --OR⁴, --NH₂, --NHR⁴, AND --N(R⁴)₂ ; M is a cation selectedfrom the group consisting of Na+, K+, Mg² ++, Ca++, Zn++, NH₄ +,alkylammonium, dialkylammonium, trialkylammonium, and tetralkylammonium;R⁴ is selected from the group consisting of H, C₁ -C₈ straight orbranched chain alkyl, N,N-dimethylaminoethyl, methyl quaternizedN,N-dimethylaminoethyl, 2-hydroxyethyl, 2-methoxyethyl, and2-ethoxyethyl; and R⁵ and R⁶ are independently selected from the groupconsisting of H, C₁ -C₈ straight or branched chain alkyl, methoxy,ethoxy, 2-hydroxyethyl, 2-methoxyethyl, and 2-ethoxyethyl; and (ii) fromabout 15% to about 50% by weight of said B units, wherein said B unitsare hydrophllic macromonomer units, copolymerizable with A, whereby saidmacromonomer units form said polymeric side chains; and wherein said Bmacromonomer units are selected from nitrogen containing macromonomersrepresented by the following structure ##STR18## where in R¹² isselected from the group consisting of hydrogen, C₁ -C₆ straight orbranched chain alkyl, benzyl, and mixtures thereof, m is an integer fromabout 10 to about 2000;E is an ethylenically unsaturated moiety,copolymerizable with A, selected from the group consisting of vinyl,allyl, acryloyl, methacryloyl, ethacryloyl syl, 2-vinyl benzyl, 3-vinylbenzyl, 4-vinyl benzyl, 2-vinylbenzoyl, 3-vinylbenzoyl, 4-vinylbenzoyl,1-butenyl, isobutenyl, isoprenyl, cyclopentenyl, cyclohexenyl, andmixtures thereof; and P is selected from the g roup consisting of hydrochloride and hydrobromide salts of2-pyridyl, 3-pyridyl, 4-pyridyl,methyl and ethyl quaternized derivatives of 2-pyridyl 3-pyridyl,4-pyridyl, and mixtures thereof;wherein said copolymer has a weightaverage molecular weight greater than about 10,000, and wherein saidcopolymer exhibits two distinct T_(g) values, said first T_(g)corresponding to said backbone and having a value from about -20° C. toabout -125° C., and said second T_(g) corresponding to said polymericside chains and having a value greater than about 25° C.